MXPA97001751A - Latex thermally sensitized - Google Patents
Latex thermally sensitizedInfo
- Publication number
- MXPA97001751A MXPA97001751A MXPA/A/1997/001751A MX9701751A MXPA97001751A MX PA97001751 A MXPA97001751 A MX PA97001751A MX 9701751 A MX9701751 A MX 9701751A MX PA97001751 A MXPA97001751 A MX PA97001751A
- Authority
- MX
- Mexico
- Prior art keywords
- latex
- monomaleate
- phm
- integer
- range
- Prior art date
Links
- 229920000126 Latex Polymers 0.000 title claims abstract description 71
- 239000004816 latex Substances 0.000 title claims abstract description 68
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- -1 polysiloxane Polymers 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 7
- 230000001804 emulsifying Effects 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 210000001268 Chyle Anatomy 0.000 claims 3
- 230000001953 sensory Effects 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 abstract description 16
- 230000000379 polymerizing Effects 0.000 abstract description 2
- 239000004745 nonwoven fabric Substances 0.000 description 14
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000004432 carbon atoms Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 241000408710 Hansa Species 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001112 coagulant Effects 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000001235 sensitizing Effects 0.000 description 3
- XLYMOEINVGRTEX-ARJAWSKDSA-M (Z)-4-ethoxy-4-oxobut-2-enoate Chemical compound CCOC(=O)\C=C/C([O-])=O XLYMOEINVGRTEX-ARJAWSKDSA-M 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 231100000202 sensitizing Toxicity 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- UXKQGJYFPNFUJY-UHFFFAOYSA-N 1-(2-methylbutan-2-yldiazenyl)cyclohexane-1-carbonitrile Chemical compound CCC(C)(C)N=NC1(C#N)CCCCC1 UXKQGJYFPNFUJY-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- WGUWOLAXPCRPKH-UHFFFAOYSA-N 2-(tert-butyldiazenyl)cyclohexane-1-carbonitrile Chemical compound CC(C)(C)N=NC1CCCCC1C#N WGUWOLAXPCRPKH-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- DLTCRVUROLYHQU-UHFFFAOYSA-N C(CCCCCCCCCCC)C1=CC=C(C=C)C=C1.C1(CCCCC1)C1=CC=C(C=C)C=C1 Chemical compound C(CCCCCCCCCCC)C1=CC=C(C=C)C=C1.C1(CCCCC1)C1=CC=C(C=C)C=C1 DLTCRVUROLYHQU-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N Ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000282941 Rangifer tarandus Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 210000002268 Wool Anatomy 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 230000001809 detectable Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N ethanolamine Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2(1H)-one Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a process for preparing a thermally sensitizable latex which is characterized by the steps of (1) polymerizing at least one conjugated diolefin monomer in an aqueous polymerization medium by free radical polymerization in the presence of an emulsifier system which it is comprised of a fatty ethoxylated monomaleate and optionally an alkyl monomaleate to produce a first latex composition, and (2) adding a water soluble organically modified polysiloxane to the first latex composition to produce the thermally sensitized latex.
Description
LATEX THERMALLY SENS I B I L I ZABLE
BACKGROUND OF THE INVENTION Latex is commonly used as a chemical binder for non-woven fabrics to provide non-gejid fabric with desired physical characteristics, such as increased resistance. The non-woven fabric is usually immersed in the latex to saturate it with the latex. If the non-woven fabric has a thickness of less than about 3 mm (millimeters), it can simply be dried to remove the water from the latex; This leaves the latex polymer dispersed through the non-woven fabric. However, in cases where the non-woven fabric is thicker than about 3 mm, the water in the latex tends to get trapped inside the non-woven fabric. To overcome this problem, thermal sensitization of latex is commonly used as the chemical agglutinant for non-woven fabrics that are thicker than approximately 3 mm. After being saturated with thermally sensitive latex, the non-woven fabrics can be heated above the latex coagulation temperature to induce coagulation. After the coagulation occurs, the water can be squeezed out of the non-woven fabric which eliminates the problem of water getting trapped inside the non-woven fabric. The rubbery polymer q disperses through the non-woven fabric, then, of course, can be cured to achieve the desired physical characteristics.
The use of thermally sensitive latexes as chemical binders for non-woven fabrics is well known. For example, U.S. Patent 4,001,162 and U.S. Patent 4,535,111 disclose that thermally sensitized latex mixtures can be used to impregnate nonwoven material and to produce hollow bodies, e.g., gloves, by the dipping process. U.S. Patent 4,535,111 also teaches that organically modified water-soluble loxanes, such as polyalcoxane oxides, can act as heat sensitizing agents. Additionally, numerous publications describe other thermal sensitizing agents, such as pol i v ini 1 alkyl ethers, polyacetale active substances with cation, polyetheramines and polyethylene oxides. US Pat. No. 4,250,071 discloses that ammonia and polyalkazole alkoxylates can be used as thermal sensitizers for rubber latexes and that the thermally detectable lipids obtained in this way are stable so that coagulation does not occur. even in case of prolognado storage or under mechanical effort. The thermostatic thermally stable latex 1 is usually synthesized by using one or more diolefin monomers, which comprise at least one carboxyl group containing onerous, and optionally additional monomers which are copolysable with the same in an emulsion containing both an anionic emulsifier as a non-ionic emulsifier. Accordingly, these thermally sensitive latices generally contain both an anionic emulsifier and a nonionic emulsifier, as well as rubbery polymer containing a monomer containing carboxy group 1 or.
SUMMARY OF THE INVENTION Using the techniques of this invention, the latices which are capable of becoming thermally stable can be synthesized without including a monomer containing carboxy group in the monomer charge composition. Consequently, the need to incorporate a monomer containing carboxyl group in the rubbery latex polymer is undermined. The need to include both an anionic emulsifier and a nonionic emulsifier in the polymerization medium is also eliminated. This invention more specifically discloses a process for preparing a thermostable thermally available latex comprising the steps of (1) polymerizing at least one conjugated diole monomer in an aqueous polymerization medium by free radical polymerization, in the presence of a emulsifying system which is comprised of a fatty ethoxylated monomaleate and, optionally, an alkyl monomaleate to produce a first latex composition; and (2) adding a modified water soluble organic polysiloxane to the first lathe composition to produce a thermally sensitive latex 1izable. The present invention also discloses a latex that can be made thermally stable, which is comprised of (1) at least one rubbery polymer, (2) water and (3) an emulsifier system that is comprised of an ethoxylated monomaleate g and optionally an alkyl monomaleate. The present invention further discloses a thermally reachable thermal latex composition which is comprised of (1 at least one rubbery polymer, (2) aGUA, 93) an emulsifier system which is comprised of ethoxylated monomaleate, and optionally an alkyl monomaleate and (4) at least one organically modified polysiloxane, soluble in water.
Detailed Description of the Invention The latices of this invention are made by a free radical emulsion polymerization process. In the process used, at least one conjugated diolefin monomer is polymerized in an aqueous polymerization medium. It is also possible to copy the conjugated diolefin monomer with additional monomers which are copolymers which can be admixed therewith, such as vinyl aromatic monomers, acrylonitrile monomers or allylpropeneic acid ester monomers. The conjugated diolefin monomer will normally contain from 4 to about 8 carbon atoms with 1,3-butadiene and isoprene being typical examples
Virtually any vinyl aromatic monomer known to polymerize in free radical systems can be polymerized with the conjugated diolefin monomers. These aromatic vinyl numbers typically contain from 8 to 20 carbon atoms. Usually, the aromatic vinyl monomer will have from 8 to 14 carbon atoms. Some representative examples of vinyl aromatic monomers that can be used include styrene, 1-v ini-1-naphthalene, 2-vinyl naphthalene, 3-methyl e-tyne, 4-propyl styrene-t-butyl styrene, 4-cyclohexyl styrene 4- dodecyl styrene, 2-et i 1 -4-benzyl 1 styrene, 4- (phenyl lbutyl 1) is reindeer and the like. Styrene is generally the most preferred vinyl aromatic monomer. The allylpropenoic acid ester monomers can also be copolymerized with the conjugated diolefin monomers to produce the latex. The monomers of acid ester to the quinolone that can be used generally have structural form 1:
R '0 CH2 = C-C-O-R
wherein R represents an alkyl group containing from 1 to 10 mos of carbon with n being an integer from 1 to 8) and wherein R 1 represents a hydrogen atom or a methyl group
(R '= C H ", with n being 0 or 1). In the cases where R1 is a n 2n + 1 methyl group, the alkyl propenoic acid ester monomer can be described more fully as a monomer of alkyl ethacrylate. The methylated methacrylate and ethanolamine, propylmethacrylate and n-butymetacrite are representative examples of alkylmetharylate groups that could be used. The alkyl group in the preferred alkyl propenoic acid ester monomer will contain from 1 to 4 carbon atoms with the alkyl groups containing 4 carbon atoms being most preferred. Consequently, the most preferred alkyl monomers, with the 1-acrylate, 1-acrylate and 1-acrylate, are the most preferred alkyl ester of propene ester, with the i 1 ato being the most preferred. The alkyl groups in said alkyl propenoic acid ester monomers may be straight or branched chain. Thus, normal propyl acrylate, iso propyl acrylate, normal butyl acrylate or tertiary butyl acrylate can be used. Normal butyl acrylate is a particularly preferred monomer. The first step of the polymerization process is carried out by adding the appropriate monomers and a very specific emulsion system to water in order to form an aqueous polymerization medium. The polymerization of the monomers is then initiated with a free radical generator. The ratio between the total amount of monomerspressed in the charge composition and water may vary between about 0.2:: 1 and about 1.2: 1. It is generally preferred that the ratio of monomers including alkyl monomaleate to water in the filler composition be within the alder scale of 0.8: 1 and approximately 1.1: 1. For example, it is usually very satisfactory to use a ratio of monomers that are not dependent on water in the charge composition that is within the range of 0.8: 1 to about 1: 1. The aqueous polymerization medium will also contain an emulsifier system which is comprised of a monomaleate of the fatty side and optionally an alkyl monomaleate. The fatty acid ethoxylated monovates that can be used will normally be of the structural formula:
0 H0 0C-CH = CH-C-0 - (- CH2-CH2-0 - ^ - (CH2 -) - CH3
where x represents an integer from 1 to approximately 30 and where y represents an integer from 5 to approximately 20. It is usually preferred that x represent an integer from 2 to 20 and stop and represent an integer from 8 to 16. Generally it is more preferred that x represent an integer from 3 to 8 and that y represent an en ro from 10 to 12. The alkyl monomaleates that can be used normally will be of the structural formula:
0 H 00C-CH = CH-C-0 (-CH2 -) ^ CH3
where n represents an integer from 0 to 7. Normally it is prefixed that n represent an integer from 1 to 4 with 1 or 2 being more preferred. The most preferred one for n is to represent 1. The fatty ethoxylated monomaleate will normally be added to the aqueous polymerization medium in an amount ranging from about 0.5 to about 6 phm (part by weight per 100 parts by weight of monomers including alkyl monomale). In this way, it will typically be present in the latex in an amount that is within the range of about 0.5 to about 6 phdl (parts by weight per 100 parts by weight of dry latex). It is usually preferred that the fatty ethoxylated maletate is present in an amount which is within the range of about 1 phm to about 4 phm. Generally, it is more preferred that the fatty ethoxylated monomaleate be present in an amount that is within the range of about 2 phm to about 3 phm. The alkyl monomaleate will normally be added to the aqueous polymerization medium in an amount that is within the range of about 0 to about 8 phm. It is usually preferred that the alkyl monomaleate be present in an amount which is within the range of about 1 phm to about 5 phm. It is generally more preferred that the alkyl moiety is present in an amount within the range of about 3 phm to about 4 phm. The precise amount of emulsifier system required in order to achieve optimal results will, of course, vary with the polymer being synthesized, with the polymerization conditions, and with the specific emulsification that is being used. For example, the polymerization reaction rate increases with higher levels of fatty ethoxylated monomaleate. Accordingly, lower reaction temperatures with increasing levels of fatty ethoxylated monomaleate will be used. In any case, people experienced in the field can easily assure the specific amount of emulsifier required in order to achieve optimal results. Essentially any type of radical generator can be used to initiate free radical emulsion polymerization. For example, chemical compounds generating free radical, ultraviolet light or radiation can be used. In order to ensure a satisfactory polymerization regime, uniformity and a controllable polymerization, radical generating chemical agents are generally used with good results. Some representative examples of free-lime initiators that are commonly used include the various peroxygen compounds such as potassium persulfate, ammonium persulphite, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, peroxide. of dicuyl, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, hydroperoxide of eumeno, p-menthane hydroperoxide, t-buoperoxyperoxide, acetone, acetone, peroxide, dicetyl, t-butyl peroxyacetate, t-butylperoxoleic acid, t-butyl peroxy-zoate, acetyl cyclohexyl-1-sulfonyl peroxide, and the like; the various azo compounds such as 2-t-but-azo-2-cyanopropane, azod ii sobutyrate dimethyl, azod ii sobutyronitrile, 2-t-butylazo-1-cyanocyclohexane, 1-t-amylazo-1-cyanocyclohexane, and the like; and the various alkaline percetals, such as 2, 2-bi s- (t-but i 1 perox i) butane, 3, 3-bi s (t-but i 1 per xi) ethyl butyrate, 1, 1 -di - (-bu lperox i) c ichexano and the others. Persulfate initiators, such as potassium persulfate and ammonium persulfate are especially useful in aqueous emulsion dispersions. The amount of initiator employed will vary with the monomers that are being polymerized and with the desired molecular weight of the polymer being synthesized. Higher molecular weights are achieved by using smaller amounts of the initiator and lower molecular weights are achieved by using larger amounts of the initiator. However, as a general rule, from 0.005 to 1 phm (parts per cent by 100 parts by weight monomer) of the initiator will be included in the reaction mixture. In the case of metal persulfate, the initials will be used more commonly from 0.1 to 0.5 phm in the polymerization medium. The free radical emulsion polymerization will typically be carried out at a temperature that is within the range of about 5QC to about 70QC. It is usually more typical for polymerization to be carried out at a temperature which is within the range of about 15 ° C to about 55 ° C. The polymerization step is allowed to continue until a very high conversion of monomers to polymer is achieved. Typically, the conversion achieved will be in excess of about 96 percent. More typically, monomer conversions in excess of about 98 percent will be achieved, with a quantitative conversion in excess of 99 percent being preferred. The solids content that is normally reached will be on the scale of about 35 percent to about 55 percent. It is usually preferred that the latex have a solids content that is within the range of about 4 percent to about 50 percent. However, the tex will normally be diluted with additional water after the polymerization but before it is used in an application as a thermally sensitive thermal tex. The thermally insensitive latex will normally be diluted to a solids content that is within the range of about 5 to about 40 percent. The latex is made thermally stable by adding at least one organically modified polysiloxane soluble in water to the latex. Said water-soluble organically modified polymers are commercially available from a variety of sources. For example, Hansa Textilchemie sells an organically water soluble polysiloxane like Hansa (R) '
Coagul ant 4710. The organically modified water soluble polysiloxane will typically be added in an amount that is within the range of about 0.1 to 1 phdl (parts by weight per 100 parts by weight of dry latex). The organically soluble polysiloxane soluble in water will typically be added to the latex in a quantity that is within the range of about 0.2 to 0.5 phdl. Generally, the coagulation temperature of the thermically sensitive latex decreases with increasing amounts of polysiloxane. The coagulation temperature of the latex also decreases with increasing levels of solids contents. Various compositional ingredients other than thermally sensitive latex 1 may also be added typically to provide the non-woven fabric being treated with the desired physical properties. For example, fillers, tackifiers, curative pigments and accelerators will typically be added to the thermically sensi bi-free latex. It can then be used as the chemical binder for virtually any type of fabric. woven natural or synthetic. For example, it can be used to treat non-woven fabrics which are comprised of polypropylene, polyethylene, cotton, wool or polyester and the like. This invention is illustrated by the following examples which are merely for the purpose of illustration and should not be construed as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, all parts and percentages are given by weight
Example 1 A grade ethoxylated monomaleate (B r i j 30 monomaleate) was synthesized by mixing 39.4 g of fatty ethoxylated alcohol having the structural formula CH 3 -CH 2) - (- 0-CH 2 -CH 2 -) - ^ - 0 H with 10.7 g. of maleic anhydride in a glass flask under gentle stirring and holding the flask at a temperature of 50 ° C overnight. An alkyl monomaleate (ethyl monomaleate) was also synthesized by mixing 21.1 g of ethanol with 45 g of maleic anhydride in a glass flask under gentle stirring and holding the flask at a temperature of 50 ° C overnight. Then a latex was synthesized using the techniques of this invention. In the procedure used, an aqueous phase was prepared by heating 1677 g of water at a temperature of 60 ° C and then adding 48 g of Brij30 monomaleate, 64 g of ethyl monomaleate, and 4.8 g of naphthalene sulfonate (a dispersion). The mixture was stirred and its pH adjusted to be within the range of 10 to 11 by the addition of potassium hydroxide. The stirring was continued until the solution became clear and had a very low viscosity. It was then charged to a 5-liter stainless steel reactor and cooled to a temperature of 35 ° C. Then, 576 g of acrylonitrile and 4.8 g of tridodecyl mercaptan were charged to the reactor. This was followed by the loading of 96 g of a 5 percent solution of triethanolamine into the reactor. After the triethanolamine was charged to the reactor, a vacuum was applied and 960 g of 1,3-butadiene were charged to the reactor. The reactor was equipped with three paddles to shake its contents that were operated at a speed of 400 rpm. After about 15 minutes of mixing at a temperature of 355C, the polymerization was initiated by injecting 160 g of a 5 percent solution of potassium persulfate into the reactor. The polymerization was allowed to continue for a period of about 8 hours after which the made latex was discharged from the reactor. The residual 1,3-butadiene monomer was separated from latex by stirring in a flask under suction for several hours. It was determined that the latex has a solids content of 46 percent, a pH of 7.4, a surface tension of 46 mN / m, a Brookfield viscosity (spindle # 1 at 60 rpm) of 25 mPa'se and a particle size at 140 nm. The nitrile rubber in the latex was determined to have a glass transition temperature of -229C. Then a thermically sensitized latex was made 1 sizable I clado 434 g of latex with 1.5 g of sodium sulfonate paraffin 1.5 g of alcohol ethoxylated fatty, 25 g of a 40 percent dispersion of zinc oxide (ZnO), and 0.2 g of polysiloxane (R) Hansa 'Coagulant 4710. Then water was added to adjust the latex to a final solids content of 30 percent with the latex being mixed for 1 hour in a 1 liter beaker equipped with a magnetic stirrer. Then, 15 g of the thermically sensitive thermal latex 1 was added to a 25 ml beaker that was placed in a bath that was maintained at a temperature of 60 ° C. The temperature at which the thermally sensible latex coagulated was observed and then recorded as 43 ° C. In another experiment, the amount of polysiloxane (R) Hansa Coagulant 4710 was increased to a level of 0.3 g. In this experiment, thermally reachable sens i bi 1 latex was coagulated at a temperature of 36 ° C.
Comparative Example 2 The polymerization procedure used in Example 1 was repeated in this experiment, except for the fact that only 3 phm of oct i lmonoma leato and no monornite of Brij 30 were used in the emulsifier system. However, in this experiment, a very low conversion of only about 52 percent resulted. It should be noted that in Example 1, the emulsifier system contained 3 phm of Br i j monomaleate 30 and 4 phm of ethyl monomaleate.
Comparative Example 3 The polymerization procedure used in Example 1 was repeated in this experiment, except for the fact that 4 phm of octylmonomaleate and 5 phm of acetoacetoxim nomaleate are used as the emulsifier system. In this experiment, overheating occurred and the latex was not evaluated.
COMPARATIVE EXAMPLE 4 The polymerization process used in Example 3 was repeated in this experiment, except for the fact that the level of oct i lmonoma leato was decreased to 3 phm. The red acid level of octi lmonoma leato decreased the polymerization rate that maintained the polymerization without overheating. However, the latex made was not thermally sensi bizable without the subsequent addition of a large amount of both nonionic and anionic emulsifiers. Although certain representative embodiments and details have been shown for the purpose of illustrating the present invention, it will be apparent to those experienced in this field that various changes and modifications may be made therein without abrogating the scope of the present invention.
Claims (10)
1. - A process for preparing a thermally slateizable latex characterized by the steps of (1) polyearizing at least one conjugated diolefin monomer in an aqueous polymerization medium by free radical polymerization in the presence of an emulsifying system which is comprised of a fatty ethoxylated monomaleate and optionally a chyle monomaleate to produce a first latex composition; and (2) administering an organically modified water-soluble polysiloxane to the first latex composition to produce thermal latex me sens ibi 1 izabl e.
2. A latex that can be made thermally insurable, characterized in that it is comprised of (1) at least one rubbery polymer, (2) water, and 3) an emulsifying system comprised of a fatty ethoxylated monomaleate. and optionally an alkyl monomaleate.
3. A thermally sensitizable latex composition characterized in that it comprises (1) when a rubbery polymer, (2) water, (3) an emulsifying system that is comprised of a fatty ethoxylated monomaleate and optionally a alkyl monomaleate and (4) at least one non-organically modified water soluble polysiloxa.
4. A latex as specified in the claim characterized in that the rubbery polymer is a nitrile rubber; wherein the fatty detoxylated monomaleate is present in the latex in an amount which is within the range of 0.5 phm to phm; wherein the alkyl monomaleate is present in the latex in an amount that is within the range of 0 to 8 phm; where the latex has a solids content that is within the range of 35 percent to 55 percent.
5. A latex as specified in the claim characterized in that the fatty ethoxylated monomaleate is of the structure for structure 1: H00 C-CH = CH-C-0 (-CH-CH -0-h- (CH0 -) - ^ CH. where x represents an integer from 1 to 30 and where y represents an integer from 5 to 20; wherein the alkyl monomaleate is from the formula 1 to structure 1: H 00 C - C H = C H - C - 0 f C H 2 H - n &H 3 - wherein n represents an integer from 0 to 4; wherein the monomalea to fatty ethoxylate is present in an amount that is within the range of 1 phm to 4 phm; and wherein the chyle monomaleate is present in an amount that is within the range of 1 phm to 5 phm.
6. A latex as specified in claim characterized in that the fatty ethoxylated monomaleate is from the structural form. H00C-CH = CH-C-0 (-CH2-CH2-0 -) - (CH2- -CH3 where x represents an integer from 2 to 20 and where y represents an integer from 8 to 16; wherein the alkyl monomaleate is of the formula structure 1: where n represents an integer from 1 to 2; wherein the monomalea to fatty ethoxylate is present in an amount that is within the range of 2 phm to 3 phm; and wherein the chyle monomaleate is present in an amount that is within the range of 3 phm to 4 phm.
7. A latex as specified in claim characterized in that the fatty ethoxylated monomaleate is of the structural formula: H 00C-CH = CH-C-0-r-CH2-CH2-0 -) - ^ - (CH2) -CH3 where x represents an integer from 3 to 8 and where y represents an integer from 10 to 12; wherein the alkyl monomaleate is of the structural formula: wherein n represents the integer 1; and where the latex has a solids content that is within the range of 40 percent to 50 percent.
8. A thermally sensitive latex as can be specified in claim 3, characterized in that 0.1 phdl to 1 phdl of the organically modified polysiloxane is present in water; where the fatty ethoxylated monomaleate is of the structural formula: H00 C-CH = CK-C- (-CH. • CH2-0 -h 'C4.-) CH and where x represents an integer from 1 to 30 v where y represents an integer of 5 23; wherein the alkyl ronomaleate is structurally 1 to 1: HOOC-C- ^ C -C- C CH 7-r ^ - H3 where n represents an integer from 0 to +; where the monomalea to eto * i I? creso is present in a quantity that is within the range of 1 hm to 4 phm; and where the monopoly of?. qu is present in a? c to 11 d? That is within the range of 1 phm to 5 ohm; wherein the polymethyl or rubbery is a nitrile rubber; and where the thermally sensible latex has a solids content that is within the range of 5 percent to &C percent.
9. A thermally sensitive latex as specified in claim 8, characterized in that the fatty acid monoether is present in an amount that is within the range of 2 phm to 3 phm; wherein the alkyl monomaleate is present in an amount which is within the range of 3 phm to 4 phm; where the monomaleate is made of the structural formula: H00C-CH = CH-C-0- -CH ¿-CH ¿-0-) x (CH ¿-) - yCH or ~ where x represents an integer from 3 to 3 and where y represents an integer from 10 to 12; and wherein the alkyl monmaleate is of the structural formula: H00C-CH = CH-C-C i-CH «¿-) - n CHo" where n represents the integer 1; and wherein thermal sensory bi-viscosity latex is comprised in addition to a filler, a c rature and an accelerator.
10. A process as specified in claim 1, wherein the polymerization is carried out at a temperature which is within the range of 5 Q C to 70 Q C; wherein the ratio between the total amount of monomers present in the charge composition and water is within the range between 0.2: 1 and 1.2: 1; wherein the emulsifying system consists only of the fatty ethoxylated monomaleate and the alkyl monomaleate.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1316496P | 1996-03-11 | 1996-03-11 | |
US013164 | 1996-03-11 | ||
US013,164 | 1996-03-11 |
Publications (2)
Publication Number | Publication Date |
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MX9701751A MX9701751A (en) | 1997-09-30 |
MXPA97001751A true MXPA97001751A (en) | 1998-07-03 |
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