CN109021237B - Large-particle-size organic siloxane rubber emulsion and plastic toughening modifier prepared from same - Google Patents
Large-particle-size organic siloxane rubber emulsion and plastic toughening modifier prepared from same Download PDFInfo
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- CN109021237B CN109021237B CN201810696706.4A CN201810696706A CN109021237B CN 109021237 B CN109021237 B CN 109021237B CN 201810696706 A CN201810696706 A CN 201810696706A CN 109021237 B CN109021237 B CN 109021237B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 48
- 239000005060 rubber Substances 0.000 title claims abstract description 48
- 239000000839 emulsion Substances 0.000 title claims abstract description 34
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229920003023 plastic Polymers 0.000 title claims abstract description 18
- 239000004033 plastic Substances 0.000 title claims abstract description 18
- 239000003607 modifier Substances 0.000 title claims abstract description 13
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- -1 propoxy, acryloxy Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims 1
- 238000004040 coloring Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- VFZRCLLDPCNXPS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8,10,10-decamethyl-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane Chemical compound C[Si]1(C)O[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 VFZRCLLDPCNXPS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a large-particle-size organosiloxane rubber emulsion and a plastic toughening modifier prepared from the same, wherein the particle size distribution range of the large-particle-size organosiloxane rubber is 400-2300 nm; the large-particle-size organosiloxane rubber is a cross-linked three-dimensional structure and has a reactivatable active group; the large-particle-size organosiloxane rubber emulsion is obtained by adopting an emulsion polymerization process. The plastic toughening modifier is obtained by emulsion polymerization of the large-particle-size organic siloxane rubber emulsion and unsaturated olefin. The large-particle-size organosiloxane rubber disclosed by the invention not only has large particle sizes, but also has a wider particle size range, so that the dispersing performance and the coloring performance of the rubber are improved, and after the active groups are added, the organosiloxane rubber can be polymerized with a plurality of high-molecular materials in later-stage application, and the problem of precipitation in later-stage modification high-temperature processing is solved.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to the field of organic siloxane rubber reaction modification.
Background
The organic silicon rubber is more and more emphasized by people because of the advantages of weather resistance, high and low temperature alternation resistance and good flame retardance, and the application range of the organic silicon rubber is wider and wider. There are also many techniques and applications for modifying other polymer materials with organosiloxane, but due to the wide variety and complex molecular structure of organosiloxane rubbers, the application fields are wide and the pertinence is very strong. Furthermore, the organosiloxane rubber has poor dispersibility, is likely to precipitate during high-temperature processing, and has very poor colorability.
The large-particle organosiloxane rubber has a wide particle size, so that the coloring performance can be improved, but the application of the large-particle organosiloxane rubber in the field of modifying copolymerized unsaturated olefin is rarely related.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the large-particle-size organosiloxane rubber emulsion is provided, has a large-particle-size emulsion with a wider distribution range, and can improve the coloring performance and the dispersing performance.
The second technical problem to be solved by the invention is: aiming at the defects in the prior art, the plastic toughening modifier is provided for toughening modification of plastics and improving the low-temperature toughness and flame retardant property of the plastics.
In order to solve the first technical problem, the technical scheme of the invention is as follows:
the large-particle-size organic siloxane rubber emulsion is characterized in that the particle size distribution range of the large-particle-size organic siloxane rubber is 400-2300 nm; the large-particle-size organosiloxane rubber is a cross-linked three-dimensional structure and has a reactivatable active group; the large-particle-size organosiloxane rubber emulsion is obtained by adopting an emulsion polymerization process.
As an improved technical scheme, the large-particle-size organosiloxane rubber emulsion is stable emulsion obtained by mixing more than one of organosilicon ring monomers with more than one of organosilicon monomers containing more than three functional groups, and then adding acid or alkali into an aqueous phase system for co-hydrolysis.
Preferably, the organosilicon cyclic monomer comprises DMC (dimethyl cyclosiloxane mixture), D4 (octamethyltetrasiloxane), D5 (decamethylcyclopentasiloxane) and D6 (decadimethyl cyclohexasiloxane).
As a preferred technical scheme, the organosilicon monomer containing more than three functional groups is an R-Si- (OR ') 3 OR R-Si- (OR') 4 organosilicon monomer; r' is methyl or ethyl; and R is any one or more of methyl, ethyl, propyl, epoxy propoxy, acryloxy and vinyl.
As a further preferred embodiment, the organosilicon monomer containing three or more functional groups is preferably tetraethoxysilane and vinyl trimethylsiloxane; the weight ratio of the ethyl orthosilicate to the vinyl trimethyl siloxane is preferably 3-6: 1-3.
According to a preferable technical scheme, the weight ratio of the water to the organosilicon monomer and the organosilicon ring monomer containing more than three functional groups is 6-8: 2-4.
Preferably, the weight ratio of the organosilicon monomer containing more than three functional groups to the organosilicon ring monomer is 0.1-1.0: 9.1-9.9.
In a more preferable embodiment, the weight ratio of the organosilicon monomer containing three or more functional groups to the organosilicon ring monomer is 0.5-0.7: 9.3-9.5.
As a preferable technical scheme, the hydrolysis temperature during hydrolysis is 20-85 ℃.
In a further preferable technical scheme, the hydrolysis temperature during hydrolysis is 40-60 ℃.
As a preferable technical scheme, the acid added during hydrolysis can be organic acid or inorganic acid, and the pH value of the water phase is adjusted to be 2-4; the added alkali can be sodium hydroxide or potassium hydroxide, and the pH value of the water phase is adjusted to be 11-12.
As a further preferable technical solution, the organic acid added during the hydrolysis is sulfonic acid, citric acid, acrylic acid, maleic acid, etc., and the inorganic acid is hydrochloric acid, sulfuric acid, phosphoric acid, etc.; more preferably citric acid; the alkali added is preferably potassium hydroxide.
In order to solve the second technical problem, the technical solution of the present invention is:
the plastic toughening modifier is obtained by emulsion polymerization of the large-particle-size organosiloxane rubber emulsion and unsaturated olefin.
Preferably, the weight ratio of the large-particle-size organosiloxane rubber to the unsaturated olefin is 5-85: 15-95.
In a more preferable embodiment, the weight ratio of the large-particle-size organosiloxane rubber to the unsaturated olefin is 5 to 50:50 to 95.
Preferably, the unsaturated olefin comprises one or more of acrylate, styrene, acrylonitrile, maleate and butadiene.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the large-particle-size organosiloxane rubber emulsion, the particle size distribution range of the large-particle-size organosiloxane rubber is 400-2300 nm; the large-particle-size organosiloxane rubber is a cross-linked three-dimensional structure and has a reactivatable active group; the modified rubber has large particle size and wider particle size range, improves the dispersing performance and the coloring performance of rubber, can be polymerized with a plurality of high polymer materials in later application after active groups are added, and solves the problem of precipitation in later modified high-temperature processing.
The large-particle-size organic siloxane rubber emulsion and unsaturated olefin are subjected to emulsion polymerization to obtain the plastic toughening modifier, which is used for toughening and modifying plastics and improving the low-temperature toughness and flame retardant property of the plastics.
Detailed Description
The invention is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The large-particle-size organosiloxane rubber emulsion is emulsion with the particle size distribution range of 1800-2000 nm, which is obtained by mixing DMC with ethyl orthosilicate and vinyl trimethyl siloxane, adding alkali (sodium hydroxide) into an aqueous phase system, and carrying out co-hydrolysis (hydrolysis temperature is 30 ℃) at the pH value of 11-12.
Example 2
The large-particle-size organosiloxane rubber emulsion is emulsion with a particle size distribution range of 1600-1800 nm, which is obtained by mixing D4 (octamethyltetrasiloxane) with ethyl orthosilicate and vinyl trimethylsiloxane in a weight ratio of 3:2, adding acid (hydrochloric acid) into an aqueous phase system to adjust the pH value of the aqueous phase to be 2-4, and carrying out co-hydrolysis (hydrolysis temperature is 35 ℃). The weight ratio of water to D4 (octamethyltetrasiloxane), ethyl orthosilicate, and vinyltrimethylsiloxane was 6: 2.
Example 3
The large-particle-size organosiloxane rubber emulsion is emulsion with a particle size distribution range of 2200-2300 nm, which is obtained by mixing D6 (decamethylcyclohexasiloxane) with ethyl orthosilicate and vinyl trimethylsiloxane in a weight ratio of 5:2, adding alkali (sodium hydroxide) into an aqueous phase system to adjust the pH of the aqueous phase to 11-12, and carrying out co-hydrolysis (hydrolysis temperature of 32 ℃). The weight ratio of water to D6 (dodecamethylcyclohexasiloxane), ethyl orthosilicate, and vinyltrimethylsiloxane was 7: 3.
Example 4
(1) 6g of citric acid is dissolved by 50 g of deionized water for later use.
(2) DMC: 93g of vinyl trimethyl siloxane, 2g of vinyl trimethyl siloxane and 5g of ethyl orthosilicate are uniformly mixed for later use.
(3) 350 g of deionized water is added into a four-neck flask with a constant temperature water bath and a stirring device, the stirring device is started to be constant speed to 100 r/min, and the temperature of the water bath is controlled at 55 ℃.
(4) Adding 100 g of mixed solution of DMC, vinyl trimethyl siloxane and ethyl orthosilicate into a four-neck flask, then adding 50 g of prepared citric acid solution after 1 minute interval, and controlling the water bath temperature at 55 ℃ to hydrolyze for 20 hours to obtain a large-particle-size organic siloxane rubber emulsion sample.
Example 5
(1) 10g of potassium hydroxide is taken and dissolved by 50 g of deionized water for standby.
(2) DMC95g, vinyl trimethyl siloxane 2g, ethyl orthosilicate 3g mixed evenly for use.
(3) 350 g of deionized water is added into a four-neck flask with a constant temperature water bath and a stirring device, the stirring device is started to be constant speed to 100 r/min, and the temperature of the water bath is controlled at 50 ℃.
(4) Adding 100 g of mixed solution of DMC, vinyl trimethyl siloxane and ethyl orthosilicate into a four-neck flask, then adding 50 g of prepared potassium hydroxide solution after 1 minute interval, and controlling the water bath temperature at 50 ℃ to hydrolyze for 20 hours to obtain a large-particle-size organic siloxane rubber emulsion sample.
Example 6
(1) 3g of hydrochloric acid is taken and dissolved by 50 g of deionized water for standby.
(2) 97g of D4 (octamethyltetrasiloxane), 97g of D6 (decadimethylcyclohexasiloxane), 3g of vinyl trimethylsiloxane and 5g of ethyl orthosilicate are uniformly mixed for later use.
(3) 350 g of deionized water was added to a four-neck flask with a constant temperature water bath, the temperature of which was controlled at 60 ℃.
(4) 100 g of mixed solution of D4 (octamethyltetrasiloxane), D6 (decadimethylcyclohexasiloxane), vinyl trimethylsiloxane and ethyl orthosilicate is added into a four-neck flask, 50 g of prepared hydrochloric acid solution is added after 1 minute interval, and the water bath temperature is controlled at 60 ℃ to hydrolyze for 20 hours to obtain a large-particle-size organosiloxane rubber emulsion sample.
Example 7
(1) 3g of sulfuric acid is taken and dissolved by 50 g of deionized water for standby.
(2) 96g of D5 (decamethylcyclopentasiloxane), 3g of vinyl trimethylsiloxane and 3g of ethyl orthosilicate are uniformly mixed for later use.
(3) 350 g of deionized water was added to a four-neck flask with a constant temperature water bath, the temperature of which was controlled at 52 ℃.
(4) 100 g of a mixed solution of D5 (decamethylcyclopentasiloxane), vinyl trimethylsiloxane and ethyl orthosilicate is added into a four-neck flask, then 52 g of prepared sulfuric acid solution is added after 1 minute interval, and the water bath temperature is controlled at 45 ℃ to hydrolyze for 20 hours to obtain a large-particle-size organosiloxane rubber emulsion sample.
Example 8
Respectively taking 500 g of the large-particle-size organosiloxane rubber emulsions obtained in the above examples 2, 4, 6 and 7, adjusting the pH to be neutral by using sodium hydroxide, then respectively carrying out thermal-initiated emulsion polymerization with 2000 g of deionized water, 500 g of butyl acrylate, 5g of sodium dodecyl sulfate and 0.5 g of potassium persulfate, controlling the reaction temperature to be 75-85 ℃, and obtaining samples 2-1, 4-1, 6-1 and 7-1 of the silicon-acrylic latex plastic toughening modifier with high coloring performance and high weather resistance after the polymerization is finished.
Example 9
Respectively taking 500 g of the large-particle-size organosiloxane rubber emulsions obtained in the above examples 1, 3 and 5, adjusting the pH value to be neutral by using citric acid, then respectively carrying out thermal-initiated emulsion polymerization with 2000 g of deionized water, 500 g of styrene, 5g of sodium dodecyl sulfate and 0.5 g of potassium persulfate, controlling the reaction temperature to be 75-85 ℃, and obtaining samples 1-1, 3-1 and 5-1 of the silicon-acrylic latex plastic toughening modifier with high coloring performance and high weather resistance after the polymerization is finished.
The prepared plastic toughening modifier can be used for toughening and modifying PC and AS plastics after being dried, and can enable the PC and AS plastics to obtain excellent low-temperature toughness and flame retardance.
The performance indexes of the toughening modifiers prepared in the above examples 8 and 9 are shown in the following table:
Claims (5)
1. the large-particle-size organic siloxane rubber emulsion is characterized in that: the particle size distribution range of the large-particle-size organosiloxane rubber is 1600-2300 nm; the large-particle-size organosiloxane rubber is a cross-linked three-dimensional structure and has a reactivatable active group; the large-particle-size organic siloxane rubber emulsion is obtained by adopting an emulsion polymerization process;
the large-particle-size organosiloxane rubber emulsion is stable emulsion obtained by mixing more than one of organosilicon ring monomers with more than one of organosilicon monomers containing more than three functional groups, and then adding acid or alkali into a water phase system for co-hydrolysis;
the acid added during hydrolysis can be organic acid or inorganic acid, and the pH value of the water phase is adjusted to be 2-4; the added alkali can be sodium hydroxide or potassium hydroxide, and the pH value of the water phase is adjusted to be 11-12;
the weight ratio of water to the organosilicon monomer and the organosilicon ring monomer containing more than three functional groups during hydrolysis is 6-8: 2-4;
the mixing weight ratio of the organosilicon monomer containing more than three functional groups to the organosilicon ring monomer is 0.1-1.0: 9.1-9.9;
the hydrolysis temperature during hydrolysis is 20-85 ℃.
2. The large particle size organosiloxane rubber emulsion of claim 1 in which: the organic silicon ring monomer comprises dimethyl cyclosiloxane mixture, D4, D5 and D6.
3. The large particle size organosiloxane rubber emulsion of claim 1 in which: the organosilicon monomer containing more than three functional groups is R-Si- (OR')3OR Si- (OR')4An organosilicon monomer; r' is methyl or ethyl; and R is any one or more of methyl, ethyl, propyl, epoxy propoxy, acryloxy and vinyl.
4. The large particle size organosiloxane rubber emulsion of claim 3 wherein: the organosilicon monomer containing more than three functional groups is preferably tetraethoxysilane and vinyl trimethoxy silane.
5. A plastic toughening modifier is characterized in that: the plastic toughening modifier is obtained by emulsion polymerization of the large-particle-size organosiloxane rubber emulsion as defined in claim 1 and unsaturated olefin.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329623A (en) * | 1998-12-04 | 2002-01-02 | 通用电气公司 | Emulsion polymerized silicone-acrylate rubber impact modifiers, thermoplastic blends, and methods for making |
| WO2005108449A1 (en) * | 2004-05-06 | 2005-11-17 | Wacker Chemie Ag | Polysiloxane graft polymer |
| CN1774463A (en) * | 2003-02-14 | 2006-05-17 | 通用电气公司 | Silicon-acrylate impact modifier |
| CN107151296A (en) * | 2017-04-18 | 2017-09-12 | 华南理工大学 | The preparation method of big particle diameter core shell structure silicone acrylates/styrol copolymer |
-
2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329623A (en) * | 1998-12-04 | 2002-01-02 | 通用电气公司 | Emulsion polymerized silicone-acrylate rubber impact modifiers, thermoplastic blends, and methods for making |
| CN1774463A (en) * | 2003-02-14 | 2006-05-17 | 通用电气公司 | Silicon-acrylate impact modifier |
| WO2005108449A1 (en) * | 2004-05-06 | 2005-11-17 | Wacker Chemie Ag | Polysiloxane graft polymer |
| CN107151296A (en) * | 2017-04-18 | 2017-09-12 | 华南理工大学 | The preparation method of big particle diameter core shell structure silicone acrylates/styrol copolymer |
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