Abstract:
The present invention disclosed a preparation method of parylene AF4, which provides a reactant and a reducing agent with the use of catalyst or exposure to UV light with photo-initiator, to shorten the reaction time as a result of minimized the byproduct(s) formation, and obtain high purity (&gt;99.0%) of parylene AF4 product under high concentrated reaction mixture.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a divisional of U.S. patent application Ser. No. 13/623,926, filed Sep. 21, 2012, which claims benefit to Taiwanese Application No. 101125578, filed Jul. 6, 2012, the entire contents of which are incorporated herein by reference. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The present invention relates to a preparation method of octafluoro-(2,2)-paracyclophane (parylene AF4) and, more particularly, the present invention relates to a catalytic or a photocatalytic preparation method of parylene AF4. 
         [0004]    2. Description of Related Art 
         [0005]    By using the vacuum pyrolysis chemical vapor deposition (CVD) method, parylene can be made into an extremely thin film which has an excellent uniformity, chemical stability and high transparency. Parylene is widely used in the forms of coating thin film, for application on the electrical isolation of printed circuit board, moisture protection of sensors or medical equipment, insulating layers of electrical unit, various protective films or packing materials, and preventing corrosion of metal coatings. 
         [0006]    Recently, due to high melting point (about 450° C.) and low dielectric constant (about 2.2) of the fluorinated parylene polymers, such as poly(tetraflouro-para-xylene) (parylene HT), with its structure shown in formula (1), compared to the traditional parylene N, parylene C, and parylene D, it has superior anti-UV properties, aging resistance, and thermal stability. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0007]    In addition, parylene HT can be coated on various irregular substrates&#39; surface, for example, glass, metal, resin, plastic, ceramic and paper. The products coated with parylene HT usually have excellent anti-corrosion, anti-moisture, and insulation protection performance, with the advantages of ultra-thin, transparent, and pinholes free, parylene HT can be used in electronic units, automotive industries, solar energy industries, and the low dielectric constant films of semiconductor industries. Currently, the coating of parylene HT is prepared via CVD process. During the CVD process, free radical monomers are produced and then polymerized into parylene HT on the surface of the object: the method is different from the other general preparation via liquid coating methods (such as dip-coating, spray-coating, sputter-coating, and plasma-coating). The coating process first includes the vaporization of fluorinated parylene dimer, such as parylene AF4 (formula (2)); then forming fluorinated para-xylene radicals by high-temperature pyrolysis; finally deposited on the coated substrate; and polymerized to poly(tetraflouro-para-xylene), which is commonly named parylene HT, as shown in formula (1), on the surface of the coated object. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0008]    The mechanism of the parylene AF4 polymerized to parylene HT via CVD is shown in formula (3). 
         [0000]    
       
                 
         
             
             
         
       
     
         [0009]    Many synthetic methods of parylene AF4 has been published in the literature, which mainly use 1,4-bis(chlorodifluoromethyl)benzene (CFB), shown in formula (4), to react with reducing agent Zinc (Zn) and obtain the parylene AF4. In the previous methods, however, in order to prevent the undesired byproducts formation, the reactions were usually carried out in highly diluted conditions, that is, large amount of solvents are necessary in the synthetic methods, therefore, the purchase and storage of the solvent, the process of feeding and the removal of the solvent or impurities will increase the cost of the preparation, coupled with long reaction time, more byproducts and complication of parylene AF4 purification procedure, those methods are not suitable for mass productions. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0010]    Therefore, there is a need for the development of a parylene AF4 (octafluoro-[2,2]-paracyclophane) preparation method characterized by high reactant concentration, short reaction time, low cost, less byproducts, easy purification, good reproducibility and stable yield. 
       SUMMARY OF THE INVENTION 
       [0011]    The present invention provides a preparation method for synthesizing parylene AF4 (octafluoro-[2,2]-paracyclophane) using catalyst or photocatalytic, which can reduce the reaction time and increase the yield of parylene AF4 by high concentrated reaction mixture. 
         [0012]    In order to achieve the objective, the preparation method of using catalyst of the present invention includes: (A) providing a reactant, a reducing agent, and a catalyst, wherein the reactant is at least one selected from the group consisting of 1,4-bis(chlorodifluoromethyl)benzene (CFB), 1,4-bis(bromodifluoromethyl)benzene (BFB), and 1,4-bis(iododifluoromethyl)benzene (IFB); the reducing agent is at least one selected from the group consisting of zinc, nickel, lead, aluminum, copper, magnesium and tin; and the catalyst is at least one selected from the group consisting of (1) an alkali metal salt, an alkali metal oxide, an alkali metal peroxide, an alkali metal hydroxide, and an alkali metal amide; (2) an alkali earth metal salt, an alkali earth metal oxide, and an alkali earth metal hydroxide; (3) a transition metal salt, a transition metal oxide, a transition metal hydroxide, and a transition metal salt containing hydrate; (4) an amphoteric element salt, an amphoteric element oxide, an amphoteric element hydroxide, an amphoteric element peroxide, and an amphoteric element salt containing hydrate; (5) a non-metallic element acid, and a non-metallic element oxide; (6) a halogen; (7) a phase transfer catalyst of quaternary ammonium salt, a phase transfer catalyst of quaternary phosphonium salt, and a phase transfer catalyst of crown ether; (B) forming a mixture by adding the reactant, the reducing agent, and the catalyst into an aprotic polar solvent; (C) heating the mixture to obtain the parylene AF4 (octafluoro-[2,2]-paracyclophane). 
         [0013]    The other preparation method of photocatalytic reaction of the present invention includes: (A) providing a reactant, and a reducing agent, wherein the reactant is at least one selected from the group consisting of 1,4-bis(chlorodifluoromethyl)benzene, 1,4-bis(bromodifluoromethyl)benzene, and 1,4-bis(iododifluoromethyl)benzene; the reducing agent is at least one selected from the group consisting of zinc, nickel, lead, aluminum, copper, magnesium and tin; (B) forming a mixture by adding the reactant and the reducing agent into an aprotic polar solvent; (C) providing an UV light source and heating the mixture to obtain the parylene AF4 (octafluoro-[2,2]-paracyclophane). Wherein, the step (B) of the above further comprises at least a photoinitiator, which is at least one selected from the group consisting of diazo compounds, peroxides, anthraquinones, phosphine oxides, and ketones. 
         [0014]    According to the preparation method of the present invention, the reactant may be single component of CFB, BFB, or IFB; or two-component mixture of CFB and BFB, CFB and IFB, or BFB and IFB; or three-component mixture of CFB, BFB and IFB. 
         [0015]    According to the preparation method of the present invention, wherein in step (B), the electrochemical potential of the reducing agent must be of the value between 0.45˜2.5 eV, and the reducing agent is at least one selected from the group consisting of zinc, nickel, lead, aluminum, copper, magnesium and tin, wherein zinc is preferable. The weight ratio of the reducing agent to the reactant is 1:1˜5, wherein 1:1.23.0 is preferable. 
         [0016]    In the method according to the present invention, the aprotic polar solvent in step (B) is at least one selected from the group consisting of N,N-dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofurane (THF), N-methylpyrrolidone (NMP), and acetonitrile (AN), wherein DMAC is preferable. The weight ratio of the reactant to the solvent is 1:1˜30, wherein 1:1.5˜10 is preferable. 
         [0017]    The method of using catalyst according to the present invention, wherein the catalyst used in step (B) is at least one selected from the group consisting of (1) an alkali metal salt, an alkali metal oxide, an alkali metal peroxide, an alkali metal hydroxide, an alkali metal amide; (2) an alkali earth metal salt, an alkali earth metal oxide, an alkali earth metal hydroxide; (3) a transition metal salt, a transition metal oxide, a transition metal hydroxide, a transition metal salt containing hydrate; (4) an amphoteric element salt, an amphoteric element oxide, an amphoteric element hydroxide, an amphoteric element peroxide, an amphoteric element salt containing hydrate; (5) a non-metallic element acid, a non-metallic element oxide; (6) a halogen; (7) a phase transfer catalyst of quaternary ammonium salt, a phase transfer catalyst of quaternary phosphonium salt, and a phase transfer catalyst of crown ether; wherein (1) the alkali metal salt are preferred to be alkali metal halide salt, alkali metal sulfate, alkali metal carbonate, alkali metal acetate, alkali metal nitrate, alkali metal amine salt, alkali metal organic salt, alkali metal phosphite, alkali metal persulfate, and alkali metal oxalate, wherein CF 3 COOLi, LiNH 2 , KH 2 PO 3 , KF, KCl, KBr, KI, CH 3 COOK, K 2 SO 4 , potassium hydrogen phthalate (KHP), potassium tert-butoxide, Na 2 SO 4 , K 2 S 2 O 8 , K 2 CO 3 , potassium acrylate, NaCl, NaI, Na 2 CO 3 , NaNH 2 , CH 3 COONa, C 2 H 5 ONa, C 6 H 5 COONa, CH 3 ONa, C 6 H 4 (OH)COONa, sodium oxalate, and CsF are more preferable, wherein CF 3 COOLi, LiNH 2 , KH 2 PO 3 , KF, KCl, KBr, KI, K 2 SO 4 , K 2 S 2 O 8 , potassium acrylate, NaCl, NaI, Na 2 SO 4 , NaNH 2 , CH 3 COONa, CH 3 ONa, sodium oxalate, and Na 2 CO 3  are most preferable; the alkali metal oxide is preferred to be Na 2 O; and the alkali metal peroxide is preferred to be Na 2 O 2 ; the alkali metal hydroxide are preferred to be LiOH, and NaOH; wherein NaOH is more preferable; the alkali metal amide is preferred to be potassium phthalimide; (2) the alkali earth metal salt are preferred to be alkali earth metal halide salt, alkali earth metal sulfate, alkali earth metal carbonate, and alkali earth metal nitrate, wherein CaCl 2 , CaCO 3 , CaSO 4 , MgCl 2 , MgSO 4 , MgCO 3 , Ba(NO 3 ) 2  and BaCl 2  are more preferable, wherein CaCl 2 , CaCO 3 , MgCl 2 , MgSO 4 , MgCO 3 , and BaCl 2  are most preferable; the alkali earth metal oxide are preferred to be MgO and CaO; the alkali earth metal hydroxide is preferred to be Ca(OH) 2 ; (3) the transition metal salt are preferred to be transition metal halide salt, transition metal acetate, transition metal sulfate, transition metal nitrate, and transition metal carbonate, wherein Ag 2 SO 4 , NiCl 2 , NiCO 3 , CuI 2 , ZnSO 4 , and ZnCl 2  are more preferable, wherein CuI 2  is most preferable; the transition metal oxide is preferred to be ZnO; the transition metal salt containing hydrate are preferred to be Zn(NO 3 ) 2 .6H 2 O, Zn(CH 3 COO) 2 .2H 2 O, Fe(NO 3 ) 3 .9H 2 O, FeCl 3 .6H 2 O, MnSO 4 .H 2 O, CuCl 2 .2H 2 O, Cu(NO 3 ) 2 .2.5H 2 O, and CoCl 2 .6H 2 O, wherein Zn(NO 3 ) 2 .6H 2 O, MnSO 4 .H 2 O, and Cu(NO 3 ) 2 .2.5H 2 O are more preferable; (4) the amphoteric element salt are preferred to be amphoteric element halide salt, amphoteric element sulfate, and amphoteric element nitrate, wherein PbCl 2 , Pb(NO 3 ) 2 , and SnCl 2  are more preferable; the amphoteric element oxide are preferred to be PbO and Pb 3 O 4 ; the amphoteric element hydroxide is preferred to be Al(OH) 3 ; the amphoteric element salt containing hydrate are preferred to be Pb(CH 3 COO) 2 .3H 2 O and Al(NO 3 ) 3 .9H 2 O, wherein Pb(CH 3 COO) 2 . 3H 2 O is more preferable; (5) the non-metallic element acid is preferred to be boric acid; the non-metallic element oxide is preferred to be P 2 O 5 ; (6) the halogen are preferred to be bromine (Br 2 ) and iodine (I 2 ); (7) the phase transfer catalyst of quaternary ammonium salt are preferred to be tetramethyl ammonium chloride (PTC-A 1 ), phenyl trimethyl ammonium chloride (PTC-A 2 ), and benzyl triethyl ammonium chloride (PTC-A 3 ), wherein PTC-A 1  and PTC-A 2  are more preferable; the phase transfer catalyst of quaternary phosphonium salt are preferred to be tetraphenyl phosphonium bromide (PTC-B 1 ) and methyl triphenyl phosphonium bromide (PTC-B 2 ), wherein PTC-B 1  is more preferable; and the phase transfer catalyst of crown ether are preferred to be 18-crown-6-ether, 12-crown-4-ether, and 15-crown-5-ether, wherein 18-crown-6-ether is more preferable. The weight ratio of catalyst to reactant is 1:10˜500. In order to shorten the reaction time, the dimerization can be accelerated by adding catalyst and also decreasing the undesired byproducts formation. 
         [0018]    The method according to the present invention, wherein in step (C), the reaction temperature is 50˜250° C., 80˜200° C. is preferred, and 100˜135° C. is more preferable. 
         [0019]    The method of using catalyst according to the present invention, wherein in step (C), the reaction time is 1˜24 hour, and 1˜12 hour is preferable. 
         [0020]    In the method of photocatalytic reaction according to the present invention, step (B) further comprises a photo-initiator, and the photo-initiator is at least one selected from the group consisting of diazo compounds such as azobisisobutyronitrile (AIBN); peroxides such as benzoyl peroxide (BPO); anthraquinones such as 2-ethylanthraquinone (EAQ); phosphine oxides such as diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (DTBPO); and ketones such as 1-hydroxy-cyclohexyl phenyl ketone (HCPK), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP), benzyl-α,α-dimethyl ketal (BDK) and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (MPMPO), wherein the weight ratio of the photo-initiator to the reactant is 1:10˜100, and 1:30˜60 is more preferable. 
         [0021]    The method of preparing parylene AF4 of the present invention, by adding at least a reactant selected from the group of CFB, BFB, and IFB into a small amount of solvent combined with a reducing agent to form a highly concentrated reaction mixture, catalyzed by adding catalyst or photocatalytic reaction with photo-initiator, and accelerated the reaction by heating to obtain parylene AF4. The capacity of parylene AF4 production is significantly increased by the high concentrated reaction mixture, therefore, the large scale of parylene AF4 manufacture promises great commercial advantages. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     Embodiment 1 
       [0022]    This embodiment involves providing a 250 ml three-necked bottle and purging with nitrogen, then adding 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.21 g (3.5 mmol) of catalyst KF, stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 135° C., the feeding time is about 2 hours and the reaction is continued for 3 hours. The crude product is filtered and washed by DMAC. The double bond-containing byproduct in filtrate is oxidized by potassium permanganate, and the filtrate is concentrated and water is added to the resulting crude solid in order to remove the inorganic substances. The crude solid obtained from filtration and recrystallized in chloroform (CHCl 3 ) to obtain 8.43 g of pure parylene AF4 (purity 99.5%, yield 40.28%). The parylene AF4 product is confirmed by analysis: the molecular weight of 352.0 g/mol is confirmed by GC/MS analysis, H 1 NMR is δ 7.1 ppm (s), and F 19  NMR is δ −118.0 ppm (s). 
       Embodiment 2 
       [0023]    In this embodiment of the present invention, a 250 ml three-necked bottle is provided and purged with nitrogen, then 50 ml of DMAC solvent is added, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.10 g (0.6 mmol) of catalyst KI, stirred and preheated to 120° C. Then the mixture of 14.82 g (0.06 mol) of reactant CFB and 1.95 g (0.006 mol) of reactant BFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 140° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 3.58 g of parylene AF4 is obtained (purity 99.63%, yield 31.0%). 
       Embodiment 3 
       [0024]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 150 ml of DMSO solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.10 g (0.6 mmol) of catalyst KI, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 131° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.34% of purity and 26.7% of yield. 
       Embodiment 4 
       [0025]    Provide a 1000 ml three-necked bottle and purge with nitrogen, then add 300 ml of DMAC solvent, 125.4 g (1.92 mol) of reducing agent zinc powder, and 1.9 g (11.4 mmol) of catalyst KI, stirred and preheated to 120° C. Then 237.0 g (0.96 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 142° C., the feeding time is about 3 hours and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 77.2 g of parylene AF4 is obtained (purity 99.7%, yield 45.7%). 
       Embodiment 5 
       [0026]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.2 g (3.4 mmol) of catalyst NaCl, stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 135° C., the feeding time is about 2 hours and the reaction is continued for 2 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 7.9 g of parylene AF4 is obtained (purity 99.52%, yield 37.44%). 
       Embodiment 6 
       [0027]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.2 g (1.4 mmol) of catalyst sodium sulfate (Na 2 SO 4 ), stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 134° C., the feeding time is about 2 hours and the reaction is continued for 2 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 7.74 g of parylene AF4 is obtained (purity 99.66%, yield 36.7%). 
       Embodiment 7 
       [0028]    This embodiment involves to providing a 250 ml three-necked bottle and purging with nitrogen, then adding 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.63 g (15.8 mmol) of catalyst sodium hydroxide (NaOH), stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 130° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 3.7 g of parylene AF4 is obtained (purity 99.28%, yield 35.24%). 
       Embodiment 8 
       [0029]    A 250 ml three-necked bottle is provided and purged with nitrogen, then added with 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.10 g (2.5 mmol) of catalyst MgO, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 130° C., the feeding time is about 1 hour and the reaction is continued for 2 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.39% of purity and 30.10% of yield. 
       Embodiment 9 
       [0030]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.20 g (1.8 mmol) of catalyst CaCl 2 , stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 132° C., the feeding time is about 2 hours and the reaction is continued for 2 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 8.36 g of parylene AF4 is obtained (purity 99.45%, yield 39.81%). 
       Embodiment 10 
       [0031]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.10 g (0.59 mmol) of catalyst MnSO 4 .1H 2 O, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 140° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.59% of purity and 31.43% of yield. 
       Embodiment 11 
       [0032]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.10 g (0.32 mmol) of catalyst CuI 2 , stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 140° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.37% of purity and 30.6% of yield. 
       Embodiment 12 
       [0033]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.20 g (2.5 mmol) of catalyst ZnO, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 132° C., the feeding time is about 1 hour and the reaction is continued for 2 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.6% of purity and 31.00% of yield. 
       Embodiment 13 
       [0034]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.10 g (1.3 mmol) of catalyst Al(OH) 3 , stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 136° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.5% of purity and 31.42% of yield. 
       Embodiment 14 
       [0035]    This embodiment of the present invention provides a 250 ml three-necked bottle and is purged with nitrogen, then adding 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.28 g (1.0 mmol) of catalyst PbCl 2 , stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 130° C., the feeding time is about 2 hours and the reaction is continued for 2 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 7.6 g of parylene AF4 is obtained with 99.46% of purity and 36.2% of yield. 
       Embodiment 15 
       [0036]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.20 g (0.53 mmol) of catalyst Pb(CH 3 COO) 2 .3H 2 O, stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 134° C., the feeding time is about 2 hours and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 6.63 g of parylene AF4 is obtained with 99.3% of purity and 31.4% of yield. 
       Embodiment 16 
       [0037]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.30 g (2.7 mmol) of catalyst PTC-A 1 , stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 136° C., the feeding time is about 2 hours and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 8.6 g of parylene AF4 is obtained with 99.45% of purity and 40.76% of yield. 
       Embodiment 17 
       [0038]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.50 g (1.4 mmol) of catalyst PTC-B 2 , stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 140° C., the feeding time is about 2 hours and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 7.53 g of parylene AF4 is obtained with 99.61% of purity and 35.7% of yield. 
       Embodiment 18 
       [0039]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 75 ml of DMAC solvent, 15.68 g (0.24 mol) of reducing agent zinc powder, and 0.40 g (1.5 mmol) of catalyst 18-crown-6, stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 136° C., the feeding time is about 2 hours and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 8.04 g of parylene AF4 is obtained with 99.72% of purity and 38.1% of yield. 
       Embodiment 19 
       [0040]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.30 g (13 mmol) of catalyst LiNH 2 , stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 136° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.41% of purity and 40.5% of yield. 
       Embodiment 20 
       [0041]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.30 g (12.5 mmol) of catalyst LiOH, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 136° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.52% of purity and 29.8% of yield. 
       Embodiments 21˜100 
       [0042]    The preparation methods, reactants, reducing agents, catalysts, solvents and the dosages, reaction temperature, reaction time and the yields of parylene AF4 of embodiments 21˜100 are shown in table 1. 
       Embodiment 101 
       [0043]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent and 7.84 g (0.12 mol) of reducing agent zinc powder, and exposed to UV light, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 134° C., the feeding time is about 1 hour and the reaction is continued for 20 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.23% of purity and 33.9% of yield. 
       Embodiment 102 
       [0044]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.30 g (1.83 mmol) of photo-initiator AIBN and then exposed to UV light, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 132° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.31% of purity and 33.3% of yield. 
       Embodiments 103˜115 
       [0045]    The preparation methods of embodiments 103˜115 are the same as embodiment 102, and their reactants, reducing agents, photo-initiators, solvents and the dosages, reaction temperature, reaction time and the yields of parylene AF4 of embodiments 103˜115 are shown in table 2. 
       Comparative Example 1 
       [0046]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 100 ml of DMAC solvent, and 31.36 g (0.48 mol) of reducing agent zinc powder, stirred and preheated to 120° C. Then 59.28 g (0.24 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 130° C., the feeding time is about 2 hours and the reaction is continued for 26 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 14.50 g of parylene AF4 is obtained with 99.33% of purity and 34.5% of yield. 
       Comparative Example 2 
       [0047]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 50 ml of DMAC solvent, 3.24 g (0.12 mol) of reducing agent aluminum powder, and 0.10 g (0.6 mmol) of catalyst KI, stirred and preheated to 120° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 138° C., the feeding time is about 1 hour and the reaction is continued for 3 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.45% of purity and 11.8% of yield. 
       Comparative Example 3 
       [0048]    A 250 ml three-necked bottle is provided and purged with nitrogen, then adding 150 ml of AN solvent, 7.84 g (0.12 mol) of reducing agent zinc powder, and 0.10 g (0.6 mmol) of catalyst KI, stirred and preheated to 80° C. Then 14.82 g (0.06 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 82.5° C., the feeding time is about 1 hour and the reaction is continued for 20 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and 1.06 g of parylene AF4 is obtained with 99.64% of purity and 10.05% of yield. 
       Comparative Example 4 
       [0049]    Provide a 250 ml three-necked bottle and purge with nitrogen, then add 100 ml of DMAC solvent, and 15.68 g (0.24 mol) of reducing agent Zinc powder, and exposed to UV light, stirred and preheated to 120° C. Then 29.64 g (0.12 mol) of reactant CFB is added dropwise to the reaction bottle, and the reaction temperature is gradually increased to 130° C., the feeding time is about 2 hour and the reaction is continued for 20 hours. The crude product is purified and analyzed by the same methods of embodiment 1 and parylene AF4 is obtained with 99.68% of purity and 35.7% of yield. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 The parylene AF4 preparation enhanced by catalyst. 
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
           
               
                   
                   
                   
                   
                   
                 Reaction 
                   
                 Parylene 
               
               
                   
                   
                 Reducing 
                   
                 Solvent 
                 temperature 
                 Reaction 
                 AF4 
               
               
                   
                 Reactant (R) 
                 agent (RA) 
                 Catalyst (X) 
                 (S) 
                 (° C.) 
                 time (hr) 
                 yield 
               
               
                 Embodiment 
                 (g/mol) 
                 (g/mol) 
                 (g/mmol) 
                 (ml) 
                 Initial/End 
                 Feed/End 
                 (%) 
               
               
                   
               
             
          
           
               
                 1 
                 CFB 
                 Zn 
                 KF 
                 DMAC 
                 120/135 
                 2/3 
                 40.28 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.21/3.5 
                 75 
                   
                   
                   
               
               
                 2 
                 CFB 
                 Zn 
                 KI 
                 DMAC 
                 120/140 
                 1/3 
                 31.0 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.6 
                 50 
                   
                   
                   
               
               
                   
                 BFB 
                   
                   
                   
                   
                   
                   
               
               
                   
                 1.95/0.006 
                   
                   
                   
                   
                   
                   
               
               
                 3 
                 CFB 
                 Zn 
                 KI 
                 DMSO 
                 120/131 
                 1/3 
                 26.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.6 
                 150  
                   
                   
                   
               
               
                 4 
                 CFB 
                 Zn 
                 KI 
                 DMAC 
                 120/142 
                 3/3 
                 45.7 
               
               
                   
                 237.0/0.96 
                 125.4/1.92 
                 1.9/11.4 
                 300  
                   
                   
                   
               
               
                 5 
                 CFB 
                 Zn 
                 NaCl 
                 DMAC 
                 120/135 
                 2/2 
                 37.44 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/3.4 
                 75 
                   
                   
                   
               
               
                 6 
                 CFB 
                 Zn 
                 Na 2 SO 4   
                 DMAC 
                 120/134 
                 2/2 
                 36.7 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.4 
                 75 
                   
                   
                   
               
               
                 7 
                 CFB 
                 Zn 
                 NaOH 
                 DMAC 
                 120/130 
                 1/3 
                 35.24 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.63/15.8 
                 50 
                   
                   
                   
               
               
                 8 
                 CFB 
                 Zn 
                 MgO 
                 DMAC 
                 120/130 
                 1/2 
                 30.1 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/2.5 
                 50 
                   
                   
                   
               
               
                 9 
                 CFB 
                 Zn 
                 CaCl 2   
                 DMAC 
                 120/132 
                 2/2 
                 39.81 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.8 
                 75 
                   
                   
                   
               
               
                 10 
                 CFB 
                 Zn 
                 MnSO 4 •1H 2 O 
                 DMAC 
                 120/140 
                 1/3 
                 31.43 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.59 
                 50 
                   
                   
                   
               
               
                 11 
                 CFB 
                 Zn 
                 CuI 2   
                 DMAC 
                 120/140 
                 1/3 
                 30.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.32 
                 50 
                   
                   
                   
               
               
                 12 
                 CFB 
                 Zn 
                 ZnO 
                 DMAC 
                 120/132 
                 1/2 
                 31.0 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.2/2.5 
                 50 
                   
                   
                   
               
               
                 13 
                 CFB 
                 Zn 
                 Al(OH) 3   
                 DMAC 
                 120/136 
                 1/3 
                 31.42 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/1.3 
                 50 
                   
                   
                   
               
               
                 14 
                 CFB 
                 Zn 
                 PbCl 2   
                 DMAC 
                 120/130 
                 2/2 
                 36.2 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.28/1.0 
                 75 
                   
                   
                   
               
               
                 15 
                 CFB 
                 Zn 
                 Pb(CH 3 COO) 2 •3H 2 O 
                 DMAC 
                 120/134 
                 2/3 
                 31.4 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/0.53 
                 75 
                   
                   
                   
               
               
                 16 
                 CFB 
                 Zn 
                 PTC-A 1   
                 DMAC 
                 120/136 
                 2/3 
                 40.76 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.3/2.7 
                 75 
                   
                   
                   
               
               
                 17 
                 CFB 
                 Zn 
                 PTC-B 2   
                 DMAC 
                 120/140 
                 2/3 
                 35.7 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.5/1.4 
                 75 
                   
                   
                   
               
               
                 18 
                 CFB 
                 Zn 
                 18-crown-6 
                 DMAC 
                 120/136 
                 2/3 
                 38.1 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.4/1.5 
                 75 
                   
                   
                   
               
               
                 19 
                 CFB 
                 Zn 
                 LiNH 2   
                 DMAC 
                 120/136 
                 1/3 
                 40.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/13 
                 50 
                   
                   
                   
               
               
                 20 
                 CFB 
                 Zn 
                 LiOH 
                 DMAC 
                 120/136 
                 1/3 
                 29.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/12.5 
                 50 
                   
                   
                   
               
               
                 21 
                 CFB 
                 Zn 
                 CF 3 CO 2 Li 
                 DMAC 
                 120/136 
                 1/3 
                 33.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/2.5 
                 50 
                   
                   
                   
               
               
                 22 
                 CFB 
                 Zn 
                 KF 
                 DMAC 
                 120/132 
                 2/2 
                 37.91 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.3/5.2 
                 75 
                   
                   
                   
               
               
                 23 
                 BFB 
                 Zn 
                 KF 
                 DMAC 
                 120/136 
                 1/2 
                 31.0 
               
               
                   
                 20.16/0.06 
                 7.84/0.12 
                 0.1/1.7 
                 50 
                   
                   
                   
               
               
                 24 
                 CFB 
                 Zn 
                 KF 
                 DMAC 
                 120/140 
                 1/3 
                 24.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/1.7 
                 50 
                   
                   
                   
               
               
                   
                 BFB 
                   
                   
                   
                   
                   
                   
               
               
                   
                 1.95/0.006 
                   
                   
                   
                   
                   
                   
               
               
                 25 
                 CFB 
                 Zn 
                 KF 
                 DMAC 
                 60/140 
                 1/3 
                 27.0 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/1.7 
                 50 
                   
                   
                   
               
               
                 26 
                 CFB 
                 Zn 
                 KCl 
                 DMAC 
                 120/135 
                 2/2 
                 33.18 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/2.7 
                 75 
                   
                   
                   
               
               
                 27 
                 CFB 
                 Zn 
                 Br 
                 DMAC 
                 120/132 
                 2/2 
                 35.55 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.7 
                 75 
                   
                   
                   
               
               
                 28 
                 CFB 
                 Zn 
                 KI 
                 DMAC 
                 120/126 
                 2/2 
                 32.7 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.5/3.0 
                 75 
                   
                   
                   
               
               
                 29 
                 BFB 
                 Zn 
                 KI 
                 DMAC 
                 120/136 
                 1/2 
                 32.0 
               
               
                   
                 20.16/0.06 
                 7.84/0.12 
                 0.1/0.6 
                 50 
                   
                   
                   
               
               
                 30 
                 CFB 
                 Zn 
                 KI 
                 DMF 
                 120/131 
                 1/3 
                 23.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.6 
                 150  
                   
                   
                   
               
               
                 31 
                 CFB 
                 Zn 
                 KI 
                 DMAC 
                 60/140 
                 1/3 
                 30.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.6 
                 50 
                   
                   
                   
               
               
                 32 
                 CFB 
                 Zn 
                 KI 
                 DMAC 
                 80/100 
                 1/5 
                 26.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.6 
                 50 
                   
                   
                   
               
               
                 33 
                 CFB 
                 Zn 
                 KI 
                 DMAC 
                 100/120 
                 1/5 
                 29.2 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.6 
                 50 
                   
                   
                   
               
               
                 34 
                 CFB 
                 Zn 
                 K 2 CO 3   
                 DMAC 
                 120/134 
                 2/2 
                 29.5 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.45 
                 75 
                   
                   
                   
               
               
                 35 
                 CFB 
                 Zn 
                 K 2 SO 4   
                 DMAC 
                 120/134 
                 2/2 
                 32.6 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.15 
                 75 
                   
                   
                   
               
               
                 36 
                 CFB 
                 Zn 
                 KH 2 PO 3   
                 DMAC 
                 120/140 
                 1/2 
                 36.2 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.83 
                 50 
                   
                   
                   
               
               
                 37 
                 CFB 
                 Zn 
                 K 2 S 2 O 8   
                 DMAC 
                 120/136 
                 2/3 
                 33.3 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/0.74 
                 75 
                   
                   
                   
               
               
                 38 
                 CFB 
                 Zn 
                 CH 3 COOK 
                 DMAC 
                 120/135 
                 1/3 
                 28.1 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/3.1 
                 50 
                   
                   
                   
               
               
                 39 
                 CFB 
                 Zn 
                 KHP 
                 DMAC 
                 120/136 
                 1/3 
                 27.9 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.5 
                 50 
                   
                   
                   
               
               
                 40 
                 CFB 
                 Zn 
                 NaCl 
                 DMAC 
                 120/138 
                 2/1 
                 34.12 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.5/8.5 
                 75 
                   
                   
                   
               
               
                 41 
                 CFB 
                 Zn 
                 NaI 
                 DMAC 
                 120/135 
                 2/2 
                 35.55 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.3 
                 75 
                   
                   
                   
               
               
                 42 
                 CFB 
                 Zn 
                 Na 2 CO 3   
                 DMAC 
                 120/134 
                 2/2 
                 35.7 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.9 
                 75 
                   
                   
                   
               
               
                 43 
                 CFB 
                 Zn 
                 Na 2 O 
                 DMAC 
                 120/135 
                 1/3 
                 32.4 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/1.6 
                 50 
                   
                   
                   
               
               
                 44 
                 CFB 
                 Zn 
                 Na 2 O 2   
                 DMAC 
                 120/136 
                 1/3 
                 37.3 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/3.85 
                 50 
                   
                   
                   
               
               
                 45 
                 CFB 
                 Zn 
                 C 2 H 5 ONa 
                 DMAC 
                 120/136 
                 1/3 
                 25.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/4.4 
                 50 
                   
                   
                   
               
               
                 46 
                 CFB 
                 Zn 
                 CH 3 COONa 
                 DMAC 
                 120/135 
                 1/3 
                 33.3 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/3.66 
                 50 
                   
                   
                   
               
               
                 47 
                 CFB 
                 Zn 
                 C 6 H 5 COONa 
                 DMAC 
                 120/136 
                 1/3 
                 29.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/2.1 
                 50 
                   
                   
                   
               
               
                 48 
                 CFB 
                 Zn 
                 CH 3 ONa 
                 DMAC 
                 120/136 
                 1/3 
                 33.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/5.6 
                 50 
                   
                   
                   
               
               
                 49 
                 CFB 
                 Zn 
                 CsF 
                 DMAC 
                 120/140 
                 1/2 
                 29.52 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.66 
                 50 
                   
                   
                   
               
               
                 50 
                 CFB 
                 Zn 
                 MgCl 2   
                 DMAC 
                 120/130 
                 2/2 
                 31.9 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/2.1 
                 75 
                   
                   
                   
               
               
                 51 
                 CFB 
                 Zn 
                 MgSO 4   
                 DMAC 
                 120/132 
                 2/2 
                 38.39 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.7 
                 75 
                   
                   
                   
               
               
                 52 
                 CFB 
                 Zn 
                 MgCO 3   
                 DMAC 
                 120/132 
                 1/2 
                 33.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/1.2 
                 50 
                   
                   
                   
               
               
                 53 
                 BFB 
                 Zn 
                 CaCl 2   
                 DMAC 
                 120/136 
                 1/2 
                 32.8 
               
               
                   
                 20.16/0.06 
                 7.84/0.12 
                 0.1/0.9 
                 50 
                   
                   
                   
               
               
                 54 
                 CFB 
                 Zn 
                 CaCl 2   
                 DMAC 
                 120/140 
                 1/3 
                 31.4 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.9 
                 50 
                   
                   
                   
               
               
                   
                 BFB 
                   
                   
                   
                   
                   
                   
               
               
                   
                 1.95/0.006 
                   
                   
                   
                   
                   
                   
               
               
                 55 
                 CFB 
                 Zn 
                 CaCl 2   
                 DMAC 
                 60/140 
                 1/3 
                 28.4 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.9 
                 50 
                   
                   
                   
               
               
                 56 
                 CFB 
                 Zn 
                 CaCO 3   
                 DMAC 
                 120/134 
                 2/2 
                 32.85 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/2.0 
                 75 
                   
                   
                   
               
               
                 57 
                 CFB 
                 Zn 
                 CaSO 4   
                 DMAC 
                 120/132 
                 1/2 
                 29.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.74 
                 50 
                   
                   
                   
               
               
                 58 
                 CFB 
                 Zn 
                 CaO 
                 DMAC 
                 120/140 
                 1/3 
                 35.24 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/1.8 
                 50 
                   
                   
                   
               
               
                 59 
                 CFB 
                 Zn 
                 Ca(OH) 2   
                 DMAC 
                 120/130 
                 1/2 
                 23.14 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/4.0 
                 50 
                   
                   
                   
               
               
                 60 
                 CFB 
                 Zn 
                 Ba(NO 3 ) 2   
                 DMAC 
                 120/136 
                 1/3 
                 29.52 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.38 
                 50 
                   
                   
                   
               
               
                 61 
                 CFB 
                 Zn 
                 BaCl 2   
                 DMAC 
                 120/140 
                 1/2 
                 34.28 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.48 
                 50 
                   
                   
                   
               
               
                 62 
                 CFB 
                 Zn 
                 FeCl 3 •6H 2 O 
                 DMAC 
                 120/136 
                 1/3 
                 25.3 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.37 
                 50 
                   
                   
                   
               
               
                 63 
                 CFB 
                 Zn 
                 Fe(NO 3 ) 3 •9H 2 O 
                 DMAC 
                 120/136 
                 1/2 
                 20.0 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.25 
                 50 
                   
                   
                   
               
               
                 64 
                 CFB 
                 Zn 
                 CoCl 2 •6H 2 O 
                 DMAC 
                 120/140 
                 1/2 
                 28.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.42 
                 50 
                   
                   
                   
               
               
                 65 
                 CFB 
                 Zn 
                 Co(NO 3 ) 2 •6H 2 O 
                 DMAC 
                 120/140 
                 1/3 
                 17.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.344 
                 50 
                   
                   
                   
               
               
                 66 
                 CFB 
                 Zn 
                 NiCl 2   
                 DMAC 
                 120/140 
                 1/3 
                 10.86 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.77 
                 50 
                   
                   
                   
               
               
                 67 
                 CFB 
                 Zn 
                 Ni(CH 3 COO) 2 •4H 2 O 
                 DMAC 
                 120/140 
                 2/3 
                 18.1 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/0.8 
                 75 
                   
                   
                   
               
               
                 68 
                 CFB 
                 Zn 
                 NiCO 3   
                 DMAC 
                 120/140 
                 1/2 
                 26.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.84 
                 50 
                   
                   
                   
               
               
                 69 
                 CFB 
                 Zn 
                 Ni—Al—Si 
                 DMAC 
                 120/140 
                 1/2 
                 36.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.5/ 
                 50 
                   
                   
                   
               
               
                 70 
                 CFB 
                 Zn 
                 Ni(NO 3 ) 2 •6H 2 O 
                 DMAC 
                 120/140 
                 1/3 
                 13.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.34 
                 50 
                   
                   
                   
               
               
                 71 
                 CFB 
                 Zn 
                 CuCl 2 •2H 2 O 
                 DMAC 
                 120/140 
                 1/3 
                 24.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.59 
                 50 
                   
                   
                   
               
               
                 72 
                 CFB 
                 Zn 
                 CuSO 4 •5H 2 O 
                 DMAC 
                 120/134 
                 1/2 
                 15.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.4 
                 50 
                   
                   
                   
               
               
                 73 
                 CFB 
                 Zn 
                 Cu(NO 3 ) 2 •2.5H 2 O 
                 DMAC 
                 120/140 
                 1/3 
                 30.96 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.43 
                 50 
                   
                   
                   
               
               
                 74 
                 CFB 
                 Zn 
                 ZnCl 2   
                 DMAC 
                 120/134 
                 1/2 
                 25.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.5/3.7 
                 50 
                   
                   
                   
               
               
                 75 
                 CFB 
                 Zn 
                 ZnSO 4   
                 DMAC 
                 120/132 
                 1/2 
                 24.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.2/1.24 
                 50 
                   
                   
                   
               
               
                 76 
                 CFB 
                 Zn 
                 Zn(NO 3 ) 2 •6H 2 O 
                 DMAC 
                 120/132 
                 1/2 
                 30.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.2/0.68 
                 50 
                   
                   
                   
               
               
                 77 
                 CFB 
                 Zn 
                 Zn(CH 3 COO) 2 •2H 2 O 
                 DMAC 
                 120/136 
                 1/3 
                 25.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.46 
                 50 
                   
                   
                   
               
               
                 78 
                 CFB 
                 Zn 
                 Ag 2 SO 4   
                 DMAC 
                 120/134 
                 1/2 
                 23.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.32 
                 50 
                   
                   
                   
               
               
                 79 
                 CFB 
                 Zn 
                 Al(NO 3 ) 3 •9H 2 O 
                 DMAC 
                 120/140 
                 1/2 
                 22.3 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.2/0.53 
                 50 
                   
                   
                   
               
               
                 80 
                 CFB 
                 Zn 
                 SnCl 2   
                 DMAC 
                 120/140 
                 2/3 
                 20.5 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/1.0 
                 75 
                   
                   
                   
               
               
                 81 
                 CFB 
                 Zn 
                 Pb(NO 3 ) 2   
                 DMAC 
                 120/130 
                 2/2 
                 26.2 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.33/1.0 
                 75 
                   
                   
                   
               
               
                 82 
                 CFB 
                 Zn 
                 PbO 
                 DMAC 
                 120/140 
                 2/2 
                 38.1 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.2/0.9 
                 75 
                   
                   
                   
               
               
                 83 
                 CFB 
                 Zn 
                 Pb 3 O 4   
                 DMAC 
                 120/136 
                 1/2 
                 32.1 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.15 
                 50 
                   
                   
                   
               
               
                 84 
                 CFB 
                 Zn 
                 (NH 4 ) 2 SiF 6   
                 DMAC 
                 120/140 
                 1/3 
                 33.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.56 
                 50 
                   
                   
                   
               
               
                 85 
                 CFB 
                 Zn 
                 P 2 O 5   
                 DMAC 
                 120/140 
                 1/2 
                 33.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.66 
                 50 
                   
                   
                   
               
               
                 86 
                 CFB 
                 Zn 
                 H 3 BO 3   
                 DMAC 
                 120/130 
                 1/3 
                 32.4 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.1/1.6 
                 50 
                   
                   
                   
               
               
                 87 
                 CFB 
                 Zn 
                 PTC-A 2   
                 DMAC 
                 120/140 
                 2/3 
                 35.7 
               
               
                   
                 29.64/0.12  
                 15.68/0.24 
                 0.43/2.5 
                 75 
                   
                   
                   
               
               
                 88 
                 CFB 
                 Zn 
                 PTC-A 3   
                 DMAC 
                 120/134 
                 2/2 
                 23.8 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.3/1.4 
                 75 
                   
                   
                   
               
               
                 89 
                 CFB 
                 Zn 
                 PTC-B 1   
                 DMAC 
                 120/135 
                 2/3 
                 37.91 
               
               
                   
                 29.64/0.12 
                 15.68/0.24 
                 0.5/1.2 
                 75 
                   
                   
                   
               
               
                 90 
                 CFB 
                 Zn 
                 12-crown-4 
                 DMAC 
                 120/140 
                 1/3 
                 32.4 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.7 
                 50 
                   
                   
                   
               
               
                 91 
                 CFB 
                 Zn 
                 15-crown-5 
                 DMAC 
                 120/140 
                 1/3 
                 35.2 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.36 
                 50 
                   
                   
                   
               
               
                 92 
                 CFB 
                 Zn 
                 NaNH 2   
                 DMAC 
                 120/135 
                 1/3 
                 32.95 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/7.7 
                 50 
                   
                   
                   
               
               
                 93 
                 CFB 
                 Zn 
                 C 6 H 4 (OH)COONa 
                 DMAC 
                 120/135 
                 1/3 
                 27.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.9 
                 50 
                   
                   
                   
               
               
                 94 
                 CFB 
                 Zn 
                 C 4 H 9 KO 
                 DMAC 
                 120/135 
                 1/3 
                 28.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/2.7 
                 50 
                   
                   
                   
               
               
                 95 
                 CFB 
                 Zn 
                 C 3 H 3 KO 2   
                 DMAC 
                 120/137 
                 1/3 
                 31.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/2.7 
                 50 
                   
                   
                   
               
               
                 96 
                 CFB 
                 Zn 
                 C 2 Na 2 O 4   
                 DMAC 
                 120/137 
                 1/3 
                 32.67 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/2.24 
                 50 
                   
                   
                   
               
               
                 97 
                 CFB 
                 Zn 
                 C 8 H 4 KNO 2   
                 DMAC 
                 120/137 
                 1/3 
                 27.9 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.62 
                 50 
                   
                   
                   
               
               
                 98 
                 CFB 
                 Zn 
                 I 2   
                 DMAC 
                 120/136 
                 1/3 
                 31.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.18 
                 50  
                   
                   
                   
               
               
                 99 
                 CFB 
                 Zn 
                 Br 2   
                 DMAC 
                 120/134 
                 1/3 
                 37.0 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.88 
                 50 
                   
                   
                   
               
               
                 100 
                 CFB 
                 Zn 
                 HCl (36%) 
                 DMAC 
                 120/134 
                 1/3 
                 18.67 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.5/5 
                 50 
                   
                   
                   
               
               
                 Comparative 
                 CFB 
                 Zn 
                 none 
                 DMAC 
                 120/130 
                 2/26 
                 34.5 
               
               
                 example 1 
                 59.28/0.24 
                 31.36/0.48 
                   
                 100  
                   
                   
                   
               
               
                 Comparative 
                 CFB 
                 Al 
                 KI 
                 DMAC 
                 120/138 
                 1/3 
                 11.8 
               
               
                 example 2 
                 14.82/0.06 
                 3.24/0.12 
                 0.1/0.6 
                 50 
                   
                   
                   
               
               
                 Comparative 
                 CFB 
                 Zn 
                 KI 
                 AN 
                 80/82.5 
                 1/20 
                 10.05 
               
               
                 example 3 
                 14.82/0.06 
                 7.84/0.12 
                 0.1/0.6 
                 150  
               
               
                   
               
               
                 Note: 
               
               
                 some abbreviation chemical name is as follows 
               
               
                 PTC-A 1  Tetramethyl ammonium chloride 
               
               
                 PTC-A 2  Phenyl trimethyl ammonium chloride 
               
               
                 PTC-A 3  Benzyl triethyl ammonium hydroxide 
               
               
                 PTC-B 1  Tetraphenylphosphonium bromide 
               
               
                 PTC-B 2  Methyl triphenylphosphonium bromide 
               
               
                 KHP Potassium hydrogen phthalate 
               
               
                 CFB 1,4-bis(chlorodifluoromethyl)Benzene 
               
               
                 BFB 1,4-bis(bromodifluoromethyl)Benzene 
               
               
                 DMAC N,N-Dimethylacetamide 
               
               
                 DMF N,N-Dimethylformamide 
               
               
                 DMSO Dimethylsulfoxide 
               
               
                 AN Acetonitrile 
               
               
                 C 4 H 9 KO Potassium tert-butoxide 
               
               
                 C 3 H 3 KO 2  Potassium acrylate 
               
               
                 C 2 Na 2 O 4  Sodium oxalate 
               
               
                 C 8 H 4 KNO 2  Potassium phthalimide 
               
               
                 K 2 S 2 O 8  Potassium persulfate 
               
               
                 Ni—Al—Si Nickel-Nickel Oxide deposited on silica-Alumina XERTEX Dohrmann(German company) product for GC packing column usage 
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 The parylene AF4 preparation accelerated by UV with photo-initiator 
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
           
               
                   
                   
                   
                   
                   
                 Reaction 
                   
                 parylene 
               
               
                   
                 Reactant 
                 Reducing 
                   
                 Solvent 
                 temperature 
                 Reaction 
                 AF4 
               
               
                   
                 (R) 
                 agent (RA) 
                 UV &amp; initiator (P) 
                 (S) 
                 (° C.) 
                 time (hr) 
                 yield 
               
               
                 Embodiment 
                 (g/mol) 
                 (g/mol) 
                 (g/mmol) 
                 (ml) 
                 Initial/End 
                 Feed/End 
                 (%) 
               
               
                   
               
               
                 101 
                 CFB 
                 Zn 
                 UV 
                 DMAC 
                 120/134 
                 1/20 
                 33.9 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                   
                 50 
                   
                   
                   
               
               
                 102 
                 CFB 
                 Zn 
                 UV + AIBN 
                 DMAC 
                 120/132 
                 1/3 
                 33.3 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.83 
                 50 
                   
                   
                   
               
               
                 103 
                 CFB 
                 Zn 
                 UV + HMPP 
                 DMAC 
                 120/136 
                 1/7 
                 37.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.83 
                 50 
                   
                   
                   
               
               
                 104 
                 CFB 
                 Zn 
                 UV + HCPK 
                 DMAC 
                 120/135 
                 1/5 
                 32.4 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.47 
                 50 
                   
                   
                   
               
               
                 105 
                 CFB 
                 Zn 
                 UV + BDK 
                 DMAC 
                 120/140 
                 1/4 
                 29.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.17 
                 50 
                   
                   
                   
               
               
                 106 
                 CFB 
                 Zn 
                 UV + BPO 
                 DMAC 
                 120/140 
                 1/4 
                 27.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.24 
                 50 
                   
                   
                   
               
               
                 107 
                 CFB 
                 Zn 
                 UV + DTBPO 
                 DMAC 
                 120/136 
                 1/4 
                 24.8 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/0.86 
                 50 
                   
                   
                   
               
               
                 108 
                 CFB 
                 Zn 
                 UV + MPMPO 
                 DMAC 
                 120/136 
                 1/4 
                 36.2 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.07 
                 50 
                   
                   
                   
               
               
                 109 
                 CFB 
                 Zn 
                 UV + EAQ 
                 DMAC 
                 120/138 
                 1/4 
                 36.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.27 
                 50 
                   
                   
                   
               
               
                 110 
                 BFB 
                 Zn 
                 UV + HMPP 
                 DMAC 
                 120/136 
                 1/3 
                 36.5 
               
               
                   
                 20.16/0.06 
                 7.84/0.12 
                 0.3/1.83 
                 50 
                   
                   
                   
               
               
                 111 
                 CFB 
                 Zn 
                 UV + HMPP 
                 DMSO 
                 120/136 
                 1/4 
                 25.7 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.83 
                 50 
                   
                   
                   
               
               
                 112 
                 CFB 
                 Zn 
                 UV + HMPP 
                 DMAC 
                 60/133 
                 1/3 
                 29.1 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.83 
                 50 
                   
                   
                   
               
               
                 113 
                 CFB 
                 Zn 
                 UV + HMPP 
                 DMAC 
                 120/136 
                 1/3 
                 27.6 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 0.3/1.83 
                 150  
                   
                   
                   
               
               
                 114 
                 CFB 
                 Zn 
                 UV + HMPP 
                 DMAC 
                 120/135 
                 1/2 
                 30.0 
               
               
                   
                 14.82/0.06 
                 15.68/0.24 
                 0.3/1.83 
                 50 
                   
                   
                   
               
               
                 115 
                 CFB 
                 Zn 
                 UV + HMPP 
                 DMAC 
                 120/134 
                 1/4 
                 30.5 
               
               
                   
                 14.82/0.06 
                 7.84/0.12 
                 1.0/6.1 
                 50 
                   
                   
                   
               
               
                 Comparative 
                 CFB 
                 Zn 
                 UV 
                 DMAC 
                 120/130 
                 2/20 
                 35.7 
               
               
                 example 4 
                 29.64/0.12 
                 15.68/0.24 
                   
                 100  
               
               
                   
               
               
                 Note: 
               
               
                 The above chemical name is as follows. 
               
               
                 AIBN 2,2-azobisisobutyronitrile 
               
               
                 HMPP 2-hydroxy-2-methyl-1-phenyl-1-propanone 
               
               
                 HCPK 1-hydroxy-cyclohexyl-phenyl ketone 
               
               
                 BDK benzyl α,α-dimethyl ketal 
               
               
                 BPO benzoyl peroxide 
               
               
                 DTBPO diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide 
               
               
                 EAQ 2-ethylanthraquinone 
               
               
                 MPMPO 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one 
               
             
          
         
       
     
         [0050]    Although the present invention has been explained in relation to its preferred embodiment, it is understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.