# Patent

## Title
Polyol compositions for hot melt adhesives

## Abstract

Disclosed are polyether and polyesters polyol condensations. The polyols are uniquely suited for ease of manufacture and improved adhesive characteristics particularly for low surface energy materials. The materials can be used in urethane adhesives.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/942,786, filed Feb. 21, 2014, which application is hereby incorporated by reference in its entirety.


FIELD OF THE INVENTION
The compositions relate to polyol materials. The polyols are polymeric acid or hydroxyl terminated materials that are end capped. The polymer polyols can be used with a reactive curing agent such as an isocyanate compounds or used in formulated curable adhesives.
BACKGROUND OF THE INVENTION
In the preparation of polyether and polyester polyol materials, and particularly in the manufacture of polyester materials, control of acid number, hydroxyl number, reaction conditions and molecular weight can be important in order to increase polyol productivity. Improved polyol materials can also produce improved adhesive properties in the formulated curable adhesive materials, including urethane adhesives.
While a number of polyether and polyester polyols have been formulated, a substantial need still exists in obtaining improved polyether and polyester polyol preparation or processing that can improve manufacturing efficiency, control of acid number or hydroxyl number and molecular weight. A further need exists to obtain improved adhesive properties in a final adhesive formulation.
BRIEF DISCLOSURE
We have found that the use of a glycidyl ether or ester compound as a capping agent can improve the manufacture of and the properties of polymer polyol compounds. Capped polyol compositions of the disclosure are substantially linear polyether or polyester polyols with an acid number equal to or less than about 2 or a hydroxyl number equal to or greater than 10 shows improved properties when used in curable (i.e.) polyurethane adhesive materials. The capped polyols when used with suitable isocyanate reactive compounds produce improved adhesive strength in bonding particularly low surface energy materials such as polyolefins and ABS resins.
The processes for manufacturing the polyol compositions and specifically polyester polyol materials are improved in terms of efficiency and yield.
Polyether polyols are typically made by polymerizing alkylene oxide materials to form substantially linear polymers.
Polyester polyols can be made by polymerizing multifunctional aliphatic or aromatic carboxylic acids (two or more carboxylic groups) with a multifunctional aliphatic or aromatic alcohol (two or more hydroxyl groups) compounds resulting in polyester materials having residual acidic or hydroxyl functionality, measured by acid number or hydroxyl number. Lower alcohol esters of the carboxylic acids can be used in the poly-esterification.
We have found that useful precursor polyester polyol materials having an acid number or hydroxyl number of about 5 to 30 can be reacted with a glycidyl compound. The amount of glycidyl compound is used that reacts with residual active hydrogen (acid or hydroxyl) to cap the polymer and complete the reaction but leaving sufficient hydroxyl to be useful in a reaction with isocyanate. The use of the glycidyl compound can also provide the manufacture of the polyol material with molecular weight control and improved adhesive properties. In the polyester, the mole ratio of hydroxyl:carboxyl (—OH:—CO2H) can be 1.2:1 to 0.8:1 or 1.1:1 to 0.9:1. The molecular weight (Mn) of the capped material is greater than 500 and is often 1000 to 16000 or 2000 to 4000.
We have further found in manufacture of polyester polyols particularly from dicarboxylic acids and di-hydroxyl compounds that the glycidyl ester compound can be used to substantially reduce manufacturing time, control molecular weight and improve the properties of the resulting adhesive materials. The use of the glycidyl capping agent results in reduced reaction time and increased productivity. The glycidyl compound permits the reaction to end before all consuming the maximum amount of the reactants. As the concentration of the reactants is reduced by the esterification, the reaction rate slows. At this point, if the molecular weight is sufficient, the glycidyl agent can be used to react with remaining active hydrogen compound to compete the synthesis. Molecular weights are measured as number average (Mn). In this way the reaction does not need to be driven to completion. Amounts of materials are selected such that the hydroxyl or acid number of the finished materials is sufficient to react with (e.g.) an isocyanate compound in a formulated adhesive.



BRIEF DESCRIPTION OF DRAWINGS
Certain viscosity and reaction characteristics of the claimed adhesives are shown in FIGS. 1 and 2, respectively.
FIG. 1 is a graph showing a relationship between viscosity and average molecular weight for a precursor (linear) polyester and a capped polyester.
FIG. 2 is a graph showing temperature versus reaction time and temperature versus weight of water collected from the reactor for several reaction conditions of Polyester 17.



DETAILED DISCUSSION
In a first aspect of the invention is a generic polymeric polyol precursor compound having an acid number or a hydroxyl number of about 5 to 30 that can be reacted with a glycidyl compound resulting in end cap of the polyol.
In another aspect of the invention, a polyether polyol can be manufactured by reacting a poly alkylene oxide polyol with the glycidyl compound.
In a further aspect of the invention, a polyester polyol can be reacted with the glycidyl compound of the invention. Substantially linear polyester polyols of dicarboxylic acids and di hydroxyl compound can be made with useful molecular weight and reactivity.
In a still further aspect of the invention, the capping agent can be used in a method for the manufacturer of a polyester polyol using substantially linear polyester polyols of dicarboxylic acids and di hydroxyl compound such as an aliphatic dicarboxylic acid, and aliphatic dihydroxy compound in order to form a preliminary polyester reaction product. When that reaction product achieves molecular weight of at least 500 or at least 2000, an acid number of 5 to 100 or, the precursor reaction product can be reacted with the glycidyl compound such as a glycidyl ester compound to complete the reaction and form the finished capped polymeric polyol material. In this way the reaction does not have to be forced to completion as the concentration of the acid and hydroxyl reactants are reduced. The amount of glycidyl compound is selected to react with acid and hydroxyl functionality leaving a finished material with an acid number (less than or equal to 2 or less than 1) or hydroxyl number (less than 6 or less than 12 or less than 112) and a residual glycidyl content of less than 0.1%, 0.05 or 0.02% for further use such as in a urethane adhesive. Since the use of the glycidyl ester compound then reacts with available acid and hydroxyl material in the reaction product, then the polyol synthesis is rapidly brought to completion much sooner than if left to simply finish by the esterification polymerization.
The invention is also directed to capped polymeric polyester polyol comprising the reaction product of a polyester polyol having a molecular weight greater than about 500. The hydroxyl number can be consistent with the levels disclosed herein. The glycidyl compound can have a formula:




wherein A is an ester or ether residue or moiety and O is oxygen and wherein A can be linear or branched, saturated or unsaturated, acyl, aliphatic or aromatic hydrocarbon radical having from 2 to 30 carbon atoms, wherein the polyol is reacted with the glycidyl compound at a ratio of epoxy groups to hydroxyl groups as disclosed herein.

Glycidyl Compounds

Glycidyl compound are shown in the structural formula I as:




wherein A is an ester or ether residue or moiety and O is oxygen. A can be linear or branched, saturated or unsaturated, acyl, aliphatic or aromatic hydrocarbon radical having from 2 to 30 carbon atoms. Alternately, glycidyl compounds, which contain glycidyl groups bonded directly to nitrogen or sulfur (where O═S or N) atoms can be employed in the process. Alkyl glycidyl ethers or esters or mixtures of alkyl glycidyl ethers or esters containing the requisite C2-30 or C4-22 alkyl substituents may be utilized for the preparation of the capped materials.

Glycidyl Ethers

Examples of alkyl glycidyl ethers include ethyl, butyl glycidyl ether, iso-butyl glycidyl ether, pentyl glycidyl ether, amyl glycidyl ether, hexyl glycidyl ether, ethyl hexyl glycidyl ether, iso-octyl glycidyl ether, n-decyl glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether, cetyl glycidyl ether, phenyl glycidyl ether benzyl etc.
Glycidyl Esters
Glycidyl esters are of the general structure set forth in structural formula I are the reaction product of one or a mixture of saturated monocarboxylic acids, preferably the alkali or tertiary ammonium salts thereof, and a halo-substituted monoepoxide.
Suitable saturated monocarboxylic acids which may be used to prepare the glycidyl esters are primary secondary and tertiary alkyl acids wherein containing 2-20 carbon atoms, more preferably 2-12 carbon atoms. Suitable such acids include neodecanoic, neotridecanoic, and pivalic acids. A particularly preferred acid is a neodecanoic acid prepared by the reaction of mono olefins averaging 8-40 carbon atoms in the molecule with carbon monoxide and water.
Suitable halo-substituted mono-epoxides which may be used to prepare the glycidyl esters include epichlorohydrin, 1-chloro-2,3-epoxyhexane, 1-chloro-2,3-epoxy-4-butyloctane, 1-chloro-2,3-epoxy heptane, 3-chloro-4,5-epoxydodecane, 3-chloro-4,5 epoxynonane, 1-chloro-2,3-epoxy-4-cyclohexyloctane and like materials.
Glycidyl esters of this type and their method of synthesis are well known in the art and are particularly described in the aforementioned U.S. Pat. No. 3,178,454 and U.S. Pat. No. 3,075,999.
Useful glycidyl esters are shown in U.S. Pat. No. 6,433,217 and are represented by the following formula II:




In the formula, R6 and R7 are typically linear or branched hydrocarbyl or alkyl groups having from about one to about 20 carbon atoms. Wherein the total carbon content of the branched alkali group of the acid group of the glycidyl ester as from about 5 to 25 carbon atoms and for certain embodiments from about 9 to about 15 carbon atoms. The glycidyl ester compositions useful in the compositions and processes disclosed herein are exemplified in the publication of Momentum entitled Cardura E10P.

Polyol for Capping Reaction

Polyols can be polyether polyols, which are made by the reaction of alkylene oxides or epoxides with active hydrogen containing starter compounds, or polyester polyols, which are made by the polycondensation of multifunctional carboxylic acids and multifunctional hydroxyl compounds.
Polyester Polyols
One useful class of polyester polyols are manufactured by the direct poly-esterification of high-purity diacids (or lower alcohol esters) and glycols, such as adipic acid and 1,4-butanediol at elevated temperature until the desired molecular weight (about 500 to 8000) is achieved. Polyester polyols are usually more expensive and more viscous than polyether polyols, but they make polyurethanes with better solvent, abrasion, and cut resistance. Other polyester polyols are based on trans-esterification (glycolysis) of poly(ethylene terephthalate) (PET) or dimethyl terephthalate (DMT) with glycols such as diethylene glycol.
Polyester polyol can be made from the following hydroxyl diols and triols reacted with dicarboxylic acid materials.










Diols and triols used for polyester polyol synthesis













Hydroxyl number,


No.
Polyol
MW, daltons
mg KOH/g










Diols










1
Ethylene glycol (EG)
62.07
1807.6


2
Diethylene glycol (DEG)
106.12
1057.2


3
1,2 Propylene glycol (PG)
76.10
1474.3


4
1,4 Butanediol (BD)
90.12
1245.0


5
Neopentyl glycol (NPG)
104.0
1078.8


6
1,6 Hexanediol
118.18
949.3


7
3-methyl-1,5-pentanediol
118
950.8



(MPD)


8
1,9-Nonanediol (ND)
160
710.3







Triols










1
Glycerol
92.10
1827.3


2
Tri-methylol propane (TMP)
122
1379.5



















Aliphatic dicarboxylic acids used for polyester polyol synthesis













Acid number,


No.
Dicarboxylic acid
MW, Daltons
mg KOH/g













1
Adipic acid (AA)
146.14
767.78


2
Glutaric acid
132.12
849.2


3
Succinic acid
118.09
950.1


4
Sebacic acid
202.0
555.4


5
Azelaic acid
186.0
603.2


6
Dodecanedioic acid
230.3
487.2



















Aromatic dicarboxylic acids and derivatives used for polyester polyol


synthesis













Acid number,


No.
Dicarboxylic acid
MW, daltons
mg KOH/g





1
Iso-phthalic acid (IPA)
166.13
675.3


2
Phthalic anhydride
148.12
757.4


3
Terephthalic acid
166.13
675.3









Polyether Polyol

Polyols use dipropylene glycol (functionality 2), glycerin (functionality 3) or a sorbitol/water solution (functionality 2.75), sucrose (functionality 8), sorbitol (functionality 6), toluene diamine (equivalent of 4 hydroxyl). Propylene oxide and/or ethylene oxide is added to the initiators until the desired molecular weight (greater than about 500 or 8000) is achieved. The order of addition and the amounts of each oxide affect many polyol properties, such as compatibility, water-solubility, and reactivity. Polyols made with only propylene oxide are terminated with secondary hydroxyl groups and are less reactive than polyols capped with ethylene oxide, which contain a higher percentage of primary hydroxyl groups.
Polyether polyols can be represented by:




Wherein R1 represents an initiator compound residue, R2 is a C2-4 alkylene group and n is a number of 2 to 100. The group R2—O— also represents a polymer residue of polymerized ethylene oxide, propylene oxide or mixtures thereof. Due to their high hydroxyl number dendritic polyols are not useful in the claimed compositions.











Initiators used for the synthesis of polyols












Molecular weight
Hydroxyl number


Starter
Functionality
(Daltons)
(mg KOH/g)













Water
2
18
6233.3


Ethylene glycol
2
62
1807.9


Diethylene glycol
2
106
1057.4


1,2 Propylene
2
76.1
1474.6


glycol


Dipropylene glycol
2
134.2
836.3


(DPG)


Glycerin
3
92
1829


Tri-methylol
3
134.2
1254.1


propane


1,2,6 Hexanetriol
3
134
1255


Triethanolamine
3
146
1152.7


Ethylenediamine
4
60
3740


Pentaerythritol
4
136.15
1648.18









Polymer Polyol Capping Reaction

The capping reaction combines a glycidyl compound with the polymer polyol and reacts the glycidyl compound with a group with an active hydrogen such as a carboxylic acid (—CO2H) or hydroxyl (—OH) group. A resulting capped polyether structures can be represented as IVa or IVb:




Capped polyester is represented by Va or Vb:





wherein R8O— represents the residue of —OH functionality of a polyether polyol or —OH functionality of a polyester polyol as structure VI:





represents a residue of the acid functionality of a polyester polyol. The glycidyl reaction creates secondary hydroxyls or primary hydroxyls depending on the presence of catalyst that can react in a urethane adhesive. Amounts of materials are selected such that the hydroxyl or carboxylic acid functionality is fully reacted and made derivative by a matching amount of glycidyl compound. At the end of the reaction little or no free carboxylic acid, epoxy or glycidyl functionality should be detected.

Adhesive Technology

The remaining active hydrogen groups, primarily hydroxyl groups, in the capped polyols can be used to formulate curing adhesives. Any curing agent that can react with the active hydrogen or hydroxyl can be used in an adhesive. Useful adhesives are urethane and epoxy materials.
Polyurethanes are produced by reacting an isocyanate containing two or more isocyanate groups with a polyol containing on average two or more hydroxyl groups per molecule typically in the presence of a catalyst.
Isocyanates are very reactive materials. Aromatic isocyanates, diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) are more reactive than aliphatic isocyanates, such as hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI). Isocyanates are difunctional; two isocyanate groups per molecule. An important exception to this is polymeric diphenyl methane diisocyanate, which is a mixture of molecules with two-, three-, and four- or more isocyanate groups. In cases like this the material has an average functionality greater than two, commonly 2.7.
The capped polyols of the disclosure that are used to make polyurethane adhesives are not “pure” compounds since they are often mixtures of similar molecules with different molecular weights and mixtures of molecules that contain different numbers of hydroxyl groups, which is why the “average functionality” is often mentioned. The polymerization reaction makes a polymer containing the urethane linkage, —RNHCOOR′— and is catalyzed by tertiary amines, such as 1,4-diazabicyclo [2.2.2] octane (also called DABCO or TEDA), DMDEE (2,2′-dimorpholino diethyl ether) and metallic compounds, such as dibutyltin dilaurate or bismuth octanoate.
Aliphatic and cycloaliphatic isocyanates are used in smaller volumes, most often in coatings and other applications where color and transparency are important. The most important aliphatic and cycloaliphatic isocyanates are 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), and 4,4′-diisocyanato dicyclohexyl methane, (H12MDI or hydrogenated MDI).
Chain extenders are low molecular weight hydroxyl and amine terminated compounds that play an important role in the polymer morphology. The choice of chain extender also determines flexural, heat, and chemical resistance properties. The most important chain extenders are ethylene glycol, 1,4-butanediol (1,4-BDO or BDO), 1,6-hexanediol, cyclohexane dimethanol and hydroquinone bis(2-hydroxyethyl) ether (HQEE).
Polyurethane catalysts can be classified into two broad categories, amine compounds and metal complexes. Traditional amine catalysts have been tertiary amines such as triethylene diamine (TEDA, 1,4-diazabicyclo[2.2.2]octane or DABCO), dimethyl cyclohexylamine (DMCHA), and dimethyl ethanolamine (DMEA). Tertiary amine catalysts are selected based on whether they drive the urethane (polyol+isocyanate, or gel) reaction or the isocyanate trimerization reaction (e.g., using potassium acetate, to form isocyanurate ring structure). Catalysts that contain a hydroxyl group or secondary amine, which react into the polymer matrix, can replace traditional catalysts thereby reducing the amount of amine that can come out of the polymer.
Suitable additives for use in the present invention may be any compound which will not interfere with the efficacy of the other components in the adhesive composition and which increases adhesion. Suitable additives include, but are not limited to, reactive or non-reactive polymers, fillers, plasticizers, viscosity control agents, defoamers and stabilizers.
Exemplary Section
The following examples and data (reflected in the figures of the conversion of the materials into polyester) show the utility of the processes of the invention in obtaining high quality polyol materials for use in the compositions of the disclosure. The preparations are exemplary of the aspect of the invention using polyester polyol materials but should not be used in unduly limiting the scope of the claims.
In the following polymerization reactions followed by the capping reaction, the reactants are combined in a conventional oil jacketed heated polyester reactor vessel equipped with a nitrogen bubbler that acts to remove volatile materials such a reaction byproduct water, reduce color formation and agitate the mixture.
In the formation of the capped polyester polyol, the dicarboxylic acid and the dihydroxyl compound is added to the vessel and heated to 140° C. Water a byproduct of esterification is formed and removed by nitrogen. After water generation slows, the temperature is gradually increased to 220° C. and the reaction is continued until the acid number falls to less than 20 preferable less than 10. At this point the molecular weight is greater than about 3000.
The reaction mixture is cooled and the glycidyl ester is then added to react with remaining acid groups. The reaction is heated to 140-190° C. This reaction forms secondary or primary hydroxyl groups with glycidyl ring opening.
Examples 1-6
Materials—
Adipic acid, CAS number 124-04-9, F.W. 146.14, melting point 150.85° C., boiling point 337.5° C., flash point 196° C.; 1,6-hexanediol, CAS number 6920-22-5, F.W. 118.18, melting point 40-42° C., boiling point 253-260° C., flash point 135° C. (Tag Closed Cup); Glycidyl ester Cardura E10P, boiling range 251-278° C. (5-95%), epoxide equivalent 240 g/mol, viscosity 7 mPa/s (23° C.), high flash point.
Synthesis of Polyester Precursor
















Molar ratio





between





hydroxyl and





carboxyl


EX. 1-6
Adipic Acid (g)
1,6-Hexanediol (g)
groups







Polyester 9,
900 (54.44 wt %)
753 (45.56 wt %)
1.035:1


11, 15, 16L, 16R


Polyester 13
900 (56.07 wt %)
705 (43.93 wt%)
0.969:1









753 g of 1,6-hexanediol (for polyester 9, 11, 15, 16L and 16R) and 900 g of adipic acid were reacted under a nitrogen atmosphere at a temperature in the range from 140 to 200° C. After water which had been formed in the reaction had been removed by distillation, the temperature was increased to range from 200-230° C. After the acid number had fallen to the expected data, the reaction was stopped. Then we measured the acid number and viscosity.














Acid
Mn (calculated
Brookfield Viscosity



Number
from
(cP, 80° C., spindle #31,


EX. 1-6
(mg KOH/g)
theory)
20 rpm)







Polyester 9
 8.22 (12 h)
3389
2432


Polyester 11
 9.10 (13 h)
3219
2064


Polyester 15
11.70 (12 h)
2802
1360


Polyester 16L
10.16 (14 h)
3035
N/A


Polyester 16R
10.56 (14 h)
2971
N/A


Polyester 13
27.24 (9 h)
2881
1600









Capping Reaction





  
    W
    
      E
      ⁢
      
        
      
      ⁢
      10
      ⁢
      
        
      
      ⁢
      P
    
  
  =
  
    
      
        
          W
          polyester
        
        *
        AN
      
      56110
    
    *
    240
    ⁢
    
      
    
    ⁢
    
      (
      g
      )
    
  




Reaction Proportions















Acid
OH number





Number of
of polyester





polyester
(mg
Wpolyester



EX. 1-6
(mg KOH/g)
KOH/g)
(g)
WE10P (g)



















Polyester 9
8.22
24.89
1221
42.93 (3.37%)


Polyester 11
9.10
25.77
1272
49.51 (3.75%)


Polyester 15
11.70
28.35
1336
66.86 (4.77%)


Polyester
10.16
26.82
1436
62.40 (4.16%)


16L


Polyester
10.56
27.22
1436
64.86 (4.32%)


16R


Polyester 13
27.24
11.72
1289
150.19 (10.44%)









Polyester precursor was heated to 160° C. in nitrogen atmosphere, and then Cardura E10P was added into the reactor in 30 minutes in droplets. The reaction temperature was increased to 190° C. in 3 hours and hold for 3 hours.


















Brookfield




OH number of
Mn
Viscosity (cP,



Acid Number
polyester (mg
(calculated from
80° C., spindle #31,


EX. 2-6
(mg KOH/g)
KOH/g)
theory)
20 rpm)







Polyester 11
0.93 (8.76)
32.63 (24.80)
3344 (3219)
2256


Polyester 15
1.22 (11.14)
36.92 (27.00)
2942 (2802)
1472


Polyester 16L
0.86 (9.73)
34.57 (25.70)
3167 (3035)
1856


Polyester 16R
1.11 (10.10)
35.03 (26.04)
3105 (2971)
1696


Polyester 13
2.00 (24.40)
32.90 (10.50)
3215 (2881)
1632









The reaction time of polyester precursor can be shortened from greater than 20 hours to to 15 hours or less. The reaction temperature of polyester precursor ranges from 140 to 230° C. and holding at 220-230° C. for not less than 9 hours. The reaction of acid carboxyl with epoxy is stoichiometric. Final reaction temperature ranges from 160-190° C. The residual epoxy in the final products is less than 0.02 mmol/g (epoxy residue is 0.032%). FIG. 1 shows the viscosity of the precursor polyester and the capped polyester.
Example 7
Materials—
Adipic acid, CAS number 124-04-9, F.W. 146.14, melting point 150.85° C., boiling point 337.5° C., flash point 196° C.; 1,6-hexanediol, CAS number 6920-22-5, F.W. 118.18, melting point 40-42° C., boiling point 253-260° C., flash point 135° C. (Tag Closed Cup); Cardura E10P, boiling range 251-278° C. (5-95%), epoxide equivalent 240 g/mol, viscosity 7 mPa/s (23° C.), high flash point.
Synthesis of Polyester Precursor
















Molar ratio





between





hydroxyl





and carboxyl


EX. 7
Adipic Acid (g)
1,6-Hexanediol (g)
groups







Polyester 17
12910 (54.45 wt %)
10800 (45.55 wt %)
1.0345:1









Reaction Procedure

10800 g of 1,6-hexanediol and 12910 g of adipic acid were reacted under a nitrogen atmosphere at a temperature in the range from 140 to 200° C. (in 5 hours). After most of the water which had been formed in the reaction had been removed by distillation, the temperature was increased to range from 220-230° C. (in 2 hours) and hold for 8.5 hours. After the acid number had fallen to the expected data, the reaction was stopped. Measure the acid number.
Results
















Acid Number
Mn



EX. 7
(mgKOH/g)
(calculated from theory)









Polyester 17
7.95 (15.5 h)
3452










Synthesis Determination of the Dosage of Cardura E10P





  
    W
    
      E
      ⁢
      
        
      
      ⁢
      10
      ⁢
      
        
      
      ⁢
      P
    
  
  =
  
    
      
        
          W
          polyester
        
        *
        AN
      
      56110
    
    *
    240
    ⁢
    
      
    
    ⁢
    
      (
      g
      )
    
  




Recipes
















Acid
OH





Number of
number of





polyester
polyester


EX. 7
(mgKOH/g)
(mgKOH/g)
Wpolyester (g)
WE10P (g)







Polyester 17
7.95
24.56
20581
697.4 (3.28%)









Reaction Procedure

Polyester precursor was cooled to 140° C. in nitrogen atmosphere, then Cardura E10P was added into the reactor in 20 minutes. The reaction temperature was increased to 180° C. in 2 hours and hold for 2 hours. Stop the reaction when the acid number below 1 mgKOH/g.
Results


















Brookfield





Mn
Viscosity (cP,



Acid
OH number of
(calculated
80° C.,



Number
polyester
from
spindle #31,


EX. 7
(mgKOH/g)
(mgKOH/g)
theory)
20 rpm)







Polyester 17
0.45
31.03
3565
3536









Reaction condition of polyester 17 (See FIG. 2 for graphical representation)














Reaction time


Condensor
H2O


(hr)
Outside T ° C.)
Inside T (° C.)
T (° C.)
wt. (g)



















−0.75
160.0
112
24
0


−0.5
160.0
122
25
0


−0.2
160.0
139
30
0


−0.08
165.6
137.7
74
0


0
165.6
136.8
95.3
0


0.5
168.3
139.5
98.5
350


1
173.9
140.4
96.2
815


1.5
179.4
148.1
92.6
1275


2
189.4
154.5
91.7
1575


2.5
199.4
167.5
91.7
1865


3
205.0
177.7
90.2
2090


3.5
210.6
186.2
85.8
2310


4
215.6
192.1
82.6
2410


4.5
221.1
197.1
77.3
2480


5
226.7
200.5
74
2530


5.5
232.2
206.1
71.5
2580


6
237.8
212.2
67.4
2615


7
237.8
221
63.1
2660


10
243.3
224.7
46
2780


12
243.3
224.4
38.8
2812


13
243.3
224.7
36.4
2825


15
243.3
223.6
34.1
2842


15.5
243.3
224
33
2846









Conclusion

The reaction time of polyester precursor can be shortened into 16 hours.
Reaction temperature of polyester precursor is range from 140 to 230° C. and holding at 220-230° C. for 8 ̃9 hours.
The reaction of carboxyl with epoxy is in stoichiometry. Reaction temperature ranges from 140-180° C. Reaction time is around 5 hours.
The residual epoxy group in the final products is less than 0.02 mmol/g (epoxy residue is 0.032%).
Adhesive
Examples

























g



Adhesive Example 1

eq. wt.
% wt
OH
NCO
800























1
Poly propylene glycol
15.750
1000
15.7500%
0.0158
x
126.00



PPG2000


2
Capped Polyester 11
22.000
1750
22.0000%
0.0126
x
176.00


3
Linear saturated Dynacol
17.500
2550
17.5000%
0.0069
x
140.00



7250 polyester polyol



EG/Hexane diol neopentyl



glycol adipic acid ester


4
CAPA5600 Capro-lactone
10.000
25000
10.0000%
0.0004
x
80.00



polyester


5
3500 HAT Hexane diol
22.000
1750
22.0000%
0.0126
x
176.00



adipic acid terephthalic acid



ester


6
BYK070 defoamer
0.100
10000000
 0.1000%
0.0000
x
0.80


7
MDI
12.600
125
12.6000%
x
0.1008
100.80


8
DMDEE
0.050
10000000
 0.0500%
x
x
0.40



(2,2′-dimorpholino



diethylether












 100.00%


800.00




100.0000
NCO %
  2.21%
0.0482
0.1008


































g



Adhesive Example 2

eq. wt.
% wt
OH
NCO
800























1
PPG2000
15.750
1000
15.7500%
0.0158
x
126.00


2
Capped polyester 13
22.000
1750
22.0000%
0.0126
x
176.00


3
Dynacol7250
17.500
2550
17.5000%
0.0069
x
140.00


4
CAPA5600
10.000
25000
10.0000%
0.0004
x
80.00


5
3500HAT
22.000
1750
22.0000%
0.0126
x
176.00


6
BYK070
0.100
10000000
 0.1000%
0.0000
x
0.80


7
MDI
12.600
125
12.6000%
x
0.1008
100.80


8
DMDEE
0.050
10000000
 0.0500%
x
x
0.40






 100.00%


800.00




100.0000
NCO %
  2.21%
0.0482
0.1008




























Comparative Adhesive





g



Example

eq. wt.
% wt
OH
NCO
800























1
PPG2000
15.750
1000
15.7500%
0.0158
x
126.00


2
3500 molecular weight
22.000
1750
22.0000%
0.0126
x
176.00



hexane-adipic acid



polyester polyol


3
Dynacol7250
17.500
2550
17.5000%
0.0069
x
140.00


4
CAPA5600
10.000
25000
10.0000%
0.0004
x
80.00


5
3500HAT
22.000
1750
22.0000%
0.0126
x
176.00


6
BYK070
0.100
10000000
 0.1000%
0.0000
x
0.80


7
MDI
12.600
125
12.6000%
x
0.1008
100.80


8
DMDEE
0.050
10000000
 0.0500%
x
x
0.40






 100.00%


800.00




100.0000
NCO %
  2.21%
0.0482
0.1008






















Adhesive Ex
Visc (250° F.) cP
Open time, Sec,
Bond ABS/Wood


















1
18850
70
Good


2
16480
100
Good


Comparative
17120
60
N/A









Comp. Ex. and Examples 1 and 2 are same percentage but Comp. Ex. is with straight molecular weight hexane-adipic acid polyester polyol Ex. 1 is with Polyester 11 (with 3-4% Cardura) and Ex. 2 is with 10% Cardura capped polyester polyols. In the case of 22% polyester polyols in the formula, with low level Cardura (3-4%), the physical property are almost the same as regular polyester polyol. With higher Cardura, the finished viscosity is a little lower but with longer open time, which is because the Cardura use reduces the crystalline behavior. Lower viscosity and longer open time are often desired in process or in application.
As can be seen in the tables of data, the processes using the compositions disclosed above produce quality polyester polyol materials in a shortened period of time with substantially complete conversion to a useful polyol material with minimal residual acid or hydroxyl minimal residual acid functionality. The hydroxyl functionality of the polyol remains since in the reaction between the glycidyl ether or glycidyl ester materials and the polyol a new hydroxyl group is formed in the reaction that remains available for reaction with the isocyanate compound in a urethane adhesive.
The claims may suitably comprise, consist of, or consist essentially of, or be substantially free of any of the disclosed or recited elements. The invention illustratively disclosed herein can also be suitably practiced in the absence of any element which is not specifically disclosed herein. The various embodiments described above are provided by way of illustration only and should not be construed to limit the claims attached hereto. Various modifications and changes may be made without following the example embodiments and applications illustrated and described herein, and without departing from the true spirit and scope of the following claims

## Claims

1. A method for the synthesis of a capped polyester polyol, the method comprising the steps of:
(a) combining a polyester polyol having a molecular weight of at least 500 with a glycidyl compound at a ratio of one glycidyl compound per each active hydroxyl group in the polyester polyol to form a mixture, wherein the polyester polyol is a reaction product of a carboxylic acid with a carboxyl functionality of two or more and a hydroxyl compound with a hydroxyl functionality of two or more, and the glycidyl compound comprises a glycidyl ether or glycidel ester compound; and
(b) reacting the polyester polyol with the glycidyl compound to form the capped material.

2. The method of claim 1, wherein the polyester polyol comprises a substantially linear aliphatic polyester.

3. The method of claim 2, wherein the aliphatic polyester is a reaction product of dicarboxylic acid and a diol.

4. The method of claim 1, wherein the polyester polyol is a reaction product of an aromatic dicarboxylic acid and a diol.

5. The method of claim 1, wherein the glycidyl ester comprises a carboxylic acid ester having 5 to 20 carbon atoms.

6. The method of claim 5, wherein the glycidyl ester comprises a compound of formula:



wherein, R6 and R7 comprises linear or branched alkyl groups having from about one to about 20 carbon atoms.

7. The method of claim 6, wherein the total carbon content of the branched alkyl group of the acid group of the glycidyl ester is such from about 9 to about 15 carbon atoms.

8. A method for the synthesis of a capped polyester polyol, the method comprising the steps of:
(a) forming a polyol from an aliphatic carboxylic acid with a carboxyl functionality of two or more and an aliphatic hydroxyl compound with a hydroxyl functionality of two or more to form a polyester polyol having a molecular weight of at least 500 by reacting the acid with the hydroxyl compound, at temperature greater than 190° C., to form a reaction mixture, until the acid number of the reaction mixture is less than 0.5; and
(b) reacting the polyester polyol with a glycidyl ester at a temperature greater than 140° C. to form the capped material.

9. A polyurethane adhesive material comprising a reaction product of an isocyanate compound and the capped polyester polyol made by the method of claim 8.

10. The polyurethane adhesive material of claim 9, wherein the isocyanate compound is MDI.