PEROXIDE CURABLE CHLORINATED POLYOLEFINS

Abstract: A curable chlorinated polyolefin elastomer composition comprising a basic metal oxide or hydroxide, such as magnesium oxide, un organic peroxide and about 0.2-10 parts per 100 parts elastomer of at least one aliphatic polyhydroxy alcohol having at least two hydroxyl groups in which the hydroxyl groups are on carbon atoms in the 1,2 or 1,3 positions relative to each other and said polyhydroxy alcohol has in molecular weight of less than about 300.

Description: TITLE Peroxide Curable Chlorinated Polyolefins BACKGROUND OF THE INVENTION In industry chlorosulfonated polyolefins are cured with sulfur or compounds that release sulfur when heated. Sulfur cures, or more precisely vulcanization, of chlorosulfonated polyolefins often results in adhesion of the rubber to the mold due to sulfur build-up on the mold cavity wall. Also, the sulfurous build-up in the mold cavity can adhere to the rubber article in the mold during vulcanization resulting in formation of discolored areas on the polymer surface. Although peroxide cures of chlorosulfonated polyolefin have been successful commercially they require relatively large amounts of inorganic acid acceptor, for example, magnesium oxide, if satisfactory physical properties are to be obtained. Large amounts of acid acceptor result in the formation of hydrochloric acid and sulfur acids during the curing process and these acids interfere with the peroxide cure. Unfortunately, the high levels of acid acceptors required to promote peroxide cures can detrimentally affect certain properties of the cured elastomer, for example, compound viscosity and water-resistance. However, when lower levels of acid acceptor are used then the compression set of peroxide-cured chlorosulfonated polyolefins is poor thus indicating that a high state of cure has not been attained. It is desirable to obtain a high state of cure of chlorinated polyethylene elastomers or chlorosulfonated polyolefin elastomers using lower levels of acid acceptor. The present invention provides a novel peroxide-curable chlorosulfonated polyolefin elastomer composition or chlorinated polyethylene elastomer composition that reaches a high state of cure by a process in which the chlorinated polyolefins are cured in the presence of certain polyhydroxy alcohols. SUMMARY OF THE INVENTION The present invention provides a chlorinated polyolefin composition having a high state of cure, --as indicated by its compression set values. More specifically this invention is directed to a curable chlorinated polyolefin elastomer composition selected from the group consisting of chlorinated polyethylene having 20-508 by weight chlorine and chlorosulfonated polyolefin having 20-50% by weight chlorine and 0.2-1.5% by weight sulfur, a basic metal oxide or hydroxide acid acceptor, an organic peroxide curing agent, and about 0.2-10 parts, preferably 1-3 parts, per 100 parts elastomer of at least one aliphatic polyhydroxy alcohol having at least two hydroxyl groups and in which the hydroxyl groups are on carbon atoms in the 1,2 or 1,3 positions relative to each other and said polyhydroxy alcohol has a molecular weight of less than about 300. Preferably, the polyhydroxy aliphatic alcohol contains 2-6 carbon atoms and the chlorosulfonated polyolefin is chlorosulfonated polyethylene. These elastomers can be used for making hose and belting but are especially useful for jacketing small diameter wire, e.g. automotive ignition wire. The-chlorinated polyolefins are cured by compounding the elastomer, the acid acceptor, organic peroxide and about 0.2 10 parts per 100 parts elastomer of at least one polyhydroxy alcohol and heating the resulting mixture to a temperature above the decomposition temperature of the peroxide and below the decomposition temperature of the elastomer until the elastomer is cured. Detailed Description of the Invention The chlorosulfonated polyolefin that is peroxide cured can be any of those well-known elastomers prepared by the reaction of a chlorosulfonating agent, such as a mixture of chlorine and sulfur dioxide gases or sulfuryl chloride, with a saturated hydrocarbon polymer, such as polyethylene, or a copolymer of ethylene with a C3-C8 alpha-olefin. The polyethylene can be either the lower density, high pressure type or the higher density homo- or copolymer type prepared with a coordination catalyst at lower pressure. The ethylene copolymers used for chlorosulfonating can contain up to about 10% by weight of C3-C8 comonomers. The number average molecular weight of the chlorosulfonated polyolefin is usually at least 10,000 The chlorosulfonation reaction is controlled to produce a polymer product which contains 20-50 percent by weight chlorine and 0.2-1.5 percent by weight sulfur, the latter being in the form of sulfonyl chloride groups attached to the saturated hydrocarbon chain. Representative polymers of this type are well known and described in, for example, U.S. Patents 2,213,786, 2,982,759 and 3,299,014. The chlorinated polyethylenes used in this invention have 20 - 50 percent by weight chlorine, and, therefore, the polymers are elastomeric. The chlorinated polyethylenes used in this invention are well-known commercial products made by reacting chlorine gas with polyethylene having a number average molecular weight greater than 10,000. The polyhydroxy alcohols used as curing aids in the composition of the present invention are added to the elastomer compositions in amounts of about 0.2-10 parts per 100 parts chlorinated polyethylene or chlorosulfonated polyolefin elastomer, and preferably 1-3 parts per 100 parts chlorinated polyethylene or chlorosulfonated polyolefin elastomer. If less than about 0.2 parts per 100 parts elastomer of polyhydroxy alcohol is used, no significant effect is seen in the state of cure of the elastomer and large amounts of acid acceptors must be used in such situations to provide a satisfactory degree of cure, and, if more than about 10 parts polyhydroxy alcohol is used per 100 parts elastomer, no further significant beneficial effects result. The polyhydroxy alcohols are aliphatic alcohols and contain hydroxyl groups on carbon atoms in the 1,2 or 1,3 positions relative to each other and have molecular weights less than about 300. The polyhydroxy alcohols used in the invention can be stibstituted with various groups such as alkoxy or carboalkoxy radicals, usually having 1-18 carbons atoms in the alkoxy radical. The molecular weight requirements pertain to the polyhydroxy alcohol only and not its equivalent ester- or ether-forming derivatives. Substitution of such radicals on the polyhydroxy alcohol does not interfere with peroxide curing. Preferably the aliphatic polyhydroxy alcohols contain 2 to 6 carbon atoms. Polyhydroxy alcohols that can be used include 2,2-dimethyl-1,3-propanediol, ethylene glycol, glycerol, 1,2-propanediol, dipentaerythritol, and pentaerythritrol,available as PE-200, a technical grade sold by Hercules, Inc., pentaerythritol monoand distearate, mono- and dilaurate, mono- and dioleate and mono- and dipalmitate. Organic peroxides used to cure elastomers can be used in this invention to cure the chlorinated polyethylene or chlorosulfonated polyolefin elastomers. Such peroxide curing agents are well known in the art and include: 2, 5-dimethyl-2, 5-di- (t-butylperoxy) hexyne-3; 2, 5-dimethyl-2 , 5-di- (t-butylperoxy) hexane; di-t-butylperoxide; 2,5-di-(t-amylperoxy)-2,5dimethyl hexane; 2,5-di(t-butylperoxy)-2,5-diphenyl hexane; 2,5-di(t-butylperoxy)-2,2,5-dicyclohexyl hexane; bis(alpha-methylbenzyl)peroxide, also called dicumyl peroxide; and dimethyl-benzyl-t-butyl peroxide; and bis-(t-butylperoxy)diisopropylbenzene. Dicumyl peroxide is preferred because of its ready availability and cost. Generally, the amount of peroxide curing agent added to the chlorinated polyolefin elastomer is about 2 to 8 parts peroxide per 100 parts elastomer and, preferably 3 to 4 parts per 100 parts elastomer. A conventional basic metal oxide or hydroxide acid acceptor is added to the chlorinated polyethylene or chlorosulfonated polyolefin compositions that are to be cured. The acid acceptor has a stabilizing effect dn the composition because hydrochloric acid (and sulfur acids in the case of chlorosulfonated polyethylene) that is generated during curing is substantially neutralized by the inorganic metal oxides or hydroxides. The metal oxides and hydroxides that are generally used are those of magnesium, calcium or lead. Magnesium oxide, calcium oxide, lead oxide and calcium hydroxide are preferred, especially magnesium oxide. The amount of acid acceptor varies depending on the particular polyhydroxy alcohol that is used in the composition and the chlorinated polyolefin to be cured. Generally, only about 0.025 - 0.25 moles of acid acceptor per 100 parts chlorosulfonated polyolefin is added to the composition and preferably about 0.05 - 0.15 moles of acid acceptor per 100 parts of chlorosulfonated polyolefin is added to the composition to obtain a satisfactory cure. When chlorinated polyethylene is cured, generally, the amount of acid acceptor used is about 0.01 - 0.1 moles per 100 parts of chlorinated polyethylene, preferably about 0.025 - 0.075 moles per 100 parts chlorinated polyethylene. As a rule the higher the amount of polyhydroxy alcohol added to the composition, the lower the amount of acid acceptor which can be used. Optionally, in addition to the peroxide curing agent a conventional coagent can be present in the elastomer composition, generally in amounts up to 6 parts per 100 parts chlorinated polyolefine, usually about 1 to 4 parts per 100 parts chlorinated polyolefin elastomer is adequate. These coagents are polyunsaturated compounds that cooperate with the peroxide curing agent to more efficiently use the peroxide. Generally, the coagents are organic compounds containing at least one, preferably two or more, aliphatic unsaturated groups, preferably allyl. Representative coagents that can be used include triallyl cyanurate, diallyl maleate and diallyl terephthalate. The chlorinated polyethylene or chlorosulfonated polyolefin composition can, and usually does, contain conventional fillers, such as carbon black, calcium carbonate, clay, silica, hydrated alumina and the like; pigments such as titanium dioxide; and stabilizers such as dialkylthiodipropionate and thiodiethylene bis[3,5-di-t-butyl-4-hydroxyhydrocinnamate], in varying amounts. The invention is illustrated by the following examples in which the proportions are given in parts by weight unless otherwise indicated. Examples 1-17 One hundred parts of curable chlorosulfonated polyethylene containing, by weight, 35t C1, 1% S is compounded on a two-roll mill with the following ingredients charged to the mill: 40 parts SRF Black, 3.2 parts dicumyl peroxide, 4 parts triallylcyanurate and metal oxide or hydroxide acid acceptor and polyhydroxy alcohol as indicated in the table below. The temperature of the mix during compounding is held below about 600C and the ingredients are uniformly mixed in about 4 minutes. The compounded stock is removed from the mill, cured for 30 minutes at 1600C, and tested as indicated. The test data show that the peroxide-cured chlorosulfonated polyethylene has excellent compression set and other satisfactory physical properties thus indicating a tight cure. INGREDIENTS PARTS PER 100 RUBBER 1 2 3 4 5 Magnesium Oxide 5a 5a 2.5a 2.5a 5a Magnesium Hydroxide Calcium oxide Calcium hydroxide Lead oxide Pentaerythr itol (PE-200) 3 2 3 1 2,2-Dimethyl-1,3 propanediol 4.6 Ethylene glycol Glycerol Mooney Scorch1 Original Minimum 25 24 20 21.5 24 10 Point Rise > 30 30 > 30 > 30 > 30 Stress-Strain-Properties (Cured 30 min/1600C) M100(MPa)2 13.4 3.1 2.2 3.4 2.2 M200(MPa)2 - 10.3 5.2 10.0 5.3 TB (MPa)2 21.7 19.0 13.6 17.9 12.4 EB (%) 140 290 535 335 565 Compression Set3 * (22 hrs/700C) 13.5 27.5 35.5 22 44.5 % (22 hrs/1210C) 26 45 72.5 51 82.5 Table (Cont'd) INGREDIENTS PARTS PER 100 RUBBER 6 7 8 9 10 Magnesium Oxide 5a 10a 10a 10a Magnesium Hydroxide 7.2b Calcium oxide Calcium hydroxide Lead oxide <RTI ID=9.1> Pentaerythr itol (PE-200) 2 1 2 3 2 2,2-Dimethyl-1,3 propanediol Ethylene glycol Glycerol Mooney Scorch Original Minimum 23 23 26 26 10 Point Rise > 30 > 30 > 30 > 30 Stress-Strain-Properties (Cured 30 min/1600C) M100(MPa)22 6.9 6.9 16.9 19.3 8.6 00 (MPa) 21.0 20.3 - TB (MPa) 24.5 23.8 23.1 25.9 23.4 EB (%) 230 230 135 135 230 Compression Set3 % (22 hrs/700C) 16 16.5 10 8 17 % (22 hrs/1210C) 38.5 38.5 29 29 Table (Cont'd.) INGREDIENTS PARTS PER 100 RUBBER 11 12 13 14 15 Magnesium Oxide 5 5 Magnesium Hydroxide Calcium oxide 7.1C 7.1c Calcium hydroxide 9.2d Lead oxide Pentaerythr itol (PE-200) 4 2 2,2-Dimethyl-1,3 propanediol Ethylene glycol 2 Glycerol 2 4 Mooney Scorch Original Minimum 10 Point Rise Stress-Strain-Properties (Cured 30 min/1600C) M100(MPa)22 1.7 10.0 15.2 15.2 13.8 M200100(MPa)22 6.5 - - - 23.5 TB (MPa) 8.6 20.7 26.2 24.8 24.2 EB (%) 780 150 140 140 145 Compression Set3 % (22 hrs/700C) 80 9 11 10 28 % (22 hrs/1210C) Table (Cont'd.) INGREDIENTS PARTS PER 100 RUBBER 16 17 Magnesium Oxide Magnesium Hydroxide Calcium oxide Calcium hydroxide Lead oxide 10e 20e Pentaerythr itol (PE-200) 2,2-Dimethyl-1,3 propanediol Ethylene glycol 6 Glycerol 4 Mooney Scorch1 Original Minimum 10 Point Rise Stress-Strain-Properties (Cured 30 min/1600C) 2 M100(MPa) 12.7 9.6 2 M200 (MPa) 2 TB (MPa) 25.5 23.8 EB (8) 170 190 Compression Set3 % (22 hrs/700C) 13 23 % (22 hrs/1210C) 1 ASTM D-1646 2 ASTM D-412 3 ASTM D-395 a. 2.5, 5 and 10 parts MgO are equivalent to 0.06, 0.12 and 0.25 moles MgO respectively. b. Equivalent to 0.12 moles Mg(OH)2 c. Equivalent to 0.13 moles CaO d. Equivalent to 0.12 moles Ca (OH)2 e. 10 and 20 parts PbO are equivalent to 0.045 and 0.09 moles PbO, respectively Examples 18-21 One hundred parts of curable chlorinated polyethylene elastomer containing 35% C1 by weight is compounded on a two-roll mill with the following ingredients charged to the mill: 40 parts SRF Black, 2.4 parts dicumyl peroxide, 1 part triallylcyanurate and metal oxide or hydroxide acid acceptor and polyhydroxy alcohol as indicated in the table below. The temperature of the mix during compounding is held below about 600C and the ingredients are uniformly mixed in about 4 minutes. The compounded stock is removed from the mill, cured for 30 minutes at 1600C and tested as indicated. The test data show that the peroxide cured chlorinated polyethylene has excellent compression set and other satisfactory physical properties thus indicating that a high degree of cure was attained. 18 19 20 21 Magnesium hydroxide - - 1.4a 0.7a Calcium Oxide 1.4b 1.5b Pentaerythritol (PE-200) 2 - 1 2 Glycerol - 1 - Stress-Strain-Properties (Cured 30 min/1600C) M100(MPa) 1 7.6 5.2 5.9 5.2 M200(MPa) 19.0 12.7 14.3 17.6 TB (MPa) 21.4 19.3 18.7 22.8 EB (%) 235 295 265 245 Compression Set2 8 (22 hrs/700C) 19 26 21 13 1. ASTM D-412 2. ASTM D-395 a. 0.7 and 1.4 parts Mg(OH)2 are equivalent to 0.012 and 0.024 moles Mg(OH)2, respectively. b. 1.4 and 1.5 parts CaO are equivalent to 0.025 and 0.027 moles CaO respectively. Examples 22-28 The procedure described above in examples 18-21 is repeated except that magnesium oxide is used as the acid acceptor, and ethylene glycol and glycerol are used in the amounts indicated as the polyhydroxy alcohols. Comparative Example 22 23 24 25 Magnesium oxide 1a 1a la la 1a (Maglite D) Pentaerythritol - 0.5 1 2 (PE-200) Glycerol - - - - 0.5 Ethylene glycol - - - - - Stress-Strain-Properties (Cured 30 min at 1600C) Original M100(MPa)1 4.5 5.9 6.3 7.4 5.6 M200(MPa)1 9.6 14.1 15.5 17.9 13.8 TB (MPa) 16.5 17.9 19.3 20.7 19.3 EB (%) 345 245 245 235 270 Compression Set % (22 hrs. at 700C) 34 26 22 20 23 Table (Cont'd.) 26 27 28 Magnesium oxide (Maglite D) la 1a la Pentaerythritol (PE-200) - - Glycerol 1 2 Ethylene glycol - - 1 Stress-Strain-Properties (Cured 30 min at 1600C) Original M100(MPa)11 6.3 7.1 6.5 M200(MPa)11 16.0 17.9 15.9 TB (MPa) 20.3 20.3 20.0 EB (%) 250 225 260 Compression Set2 % (22 hrs/700C) 24 19 22 1 ASTM D-412 2 ASTM D-395 a. Equivalent to 0.025 moles MgO

Claims: CLAIMS ¯ ¯ ¯ r 1. A curable chlorinated polyolefin elastomer composition selected from the group consisting of chlorinated polyethylene having 20-50% chlorine by weight and chlorosulfonated polyolefin having 20-50% chlorine by weight and 0.2-1.5% sulfur by weight, a basic metal oxide or hydroxide acid acceptor, an organic peroxide curing agent, and about 0.2-10 parts per 100 parts elastomer of at least one aliphatic polyhydroxy alcohol having at least two hydroxyl groups and in which the hydroxyl groups are on carbon atoms in the 1,2 or 1,3 positions relative to each other and said polyhydroxy alcohol has a molecular weight of less than about 300. 2. A composition of claim 1 where the chlorinated polyolefin is chlorosulfonated polyolefin and the basic metal oxide or hydroxide acid acceptor is present in the composition in an amount of about 0.025-0.25 moles acid acceptor per 100 parts chlorosulfonated polyolefin. 3. A composition of claim 1 where the chlorinated polyolefin is chlorinated polyethylene and the basic metal oxide or hydroxide acid acceptor is present in the composition in an amount of about 0.01-0.1 moles per 100 parts chlorinated polyethylene. 4. A composition of claims 1, 2 or 3 where the polyhydroxy alcohol contains 2-6 carbon atoms. 5. A composition of claims 1, 2 or 3 where the acid acceptor is an oxide or hydroxide of magnesium. 6. A composition of claims 1 or 2 where the chlorosulfonated polyolefin elastomer is chlorosulfonated polyethylene or chlorinated polyethylene. 7. A composition of claims 1 to 6, where the polyhydroxy alcohol is selected from ethylene glycol, glycerol, and Pentaerythritol. 8. A process for curing a chlorinated polyolefin elastomer composition selected from the group consisting of chlorinated polyethylene having 20-508 chlorine by weight and chlorosulfonated polyolefin having 20-508 chlorine by weight and 0.2-1.5% sulfur by weight comprising compounding said elastomer, a basic metal oxide or hydroxide acid acceptor, an organic peroxide curing agent and about 0.2-10 parts per 100 parts elastomer of at least one aliphatic polyhydroxy alcohol having at least two hydroxyl groups in which the hydroxyl groups are in the 1,2 or 1,3 positions relative to each other, and said polyhydroxy alcohol has a molecular weight of less than about 300 and heating the resulting mixture to a temperature above the decomposition temperature of the peroxide and below the decomposition temperature of the elastomer until the elastomer is cured. 9. A process of claim 8, wherein about 0.025 - 0.25 moles, preferably 0.01 - 0.1 moles of acid acceptor per 100 parts chlorosulfonated polyolefin are added to the mixture. 10. A process of claims 8 and 9 where the polyhydroxy alcohol contains 2- 6 carbon atoms. 11. A process of claims 8 - 10 where the acid acceptor is an oxide or hydroxide of magnesium 12. A process of claims 8 - 11 where the chlorosulfonated polyolefin elastomer is chlorosulfonated polyethylene or chlorinated polyethylene. 13. A process of claims 8 to 12 where the polyhydroxy alcohol is selected from ethylene glycol, glycerol, and pentarythrithol.

Inventors: HONSBERG, WOLFGANG
Applicants: E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1983
Main classification: C08J3
IPC codes: C08L1, C08K5, C08K3, C08L101, C08L27, C08L23