CN108659156A - The preparation method of automobile coating thermoplastic acrylic resin - Google Patents
The preparation method of automobile coating thermoplastic acrylic resin Download PDFInfo
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- CN108659156A CN108659156A CN201810522243.XA CN201810522243A CN108659156A CN 108659156 A CN108659156 A CN 108659156A CN 201810522243 A CN201810522243 A CN 201810522243A CN 108659156 A CN108659156 A CN 108659156A
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- acrylic resin
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- thermoplastic acrylic
- automobile coating
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 42
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 41
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 38
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000011248 coating agent Substances 0.000 title claims abstract description 23
- 238000000576 coating method Methods 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 15
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 14
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- 125000004386 diacrylate group Chemical group 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- -1 silica Alkane Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000002148 esters Chemical group 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- QNLFWRVSLRGSJN-UHFFFAOYSA-N 2-methylidene-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical class C=[Si]1O[SiH2]O[SiH2]O[SiH2]O1 QNLFWRVSLRGSJN-UHFFFAOYSA-N 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- 150000002527 isonitriles Chemical class 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 13
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical class C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of preparation methods of automobile coating thermoplastic acrylic resin, first double bond containing organosiloxane monomer is copolymerized with acrylic monomers in the presence of initiator, then the hydrophobic compound of copolymerization product and low surface tension is compound, obtains organic siloxane modified thermoplastic acrylic resin.Acrylic resin molecular weight prepared by the present invention is big, and resin viscosity is big, has better wear-resisting and water resistance compared to common thermoplastic acrylic resin, after film forming.Due to the presence of low surface tension chain link, smooth performance is able to larger raising, has better rapid draing, suitable for the application of vehicle chassis.
Description
Technical field
The present invention relates to a kind of preparation methods of acrylic resin, and in particular to a kind of organic siloxane modified automobile coating use
The method of thermoplastic acrylic resin.
Background technology
Film-forming resin of the thermoplastic acrylic resin as volatility weatherability coating, due to easy for construction, by coating
The favor of industry.For presently commercially available thermoplastic acrylic resin in order to easy for construction, molecular weight is not generally high, mostly uses solwution method
Synthesis；However intensity, the compactness of coating are not satisfactory after the thermoplastic resin film forming of the small-molecular-weight of solwution method synthesis, with
Very poor with wearability as water resistance, application range is often very narrow.
In order to enhance the performance of acrylic resin, Chinese patent literature CN107033296A（Application number
201710318628.X）Disclosing the extra-weather-proof polysiloxane-modified acrylic resin of one kind and finishing coat preparation method, the resin is
By 15~20 parts of silester, 20~35 parts of vinyltriethoxysilane, 1~8 part of catalyst, 35~56 parts of olefin(e) acid esters lists
Body and 0.8~5 part of initiator composition.Preparation method includes the following steps:The first step：By the silester and second of the component
Alkenyl triethoxysilane be uniformly mixed, be warming up to 70~90 DEG C later and be slowly added under the temperature condition catalyst into
Row 2~5h of reaction, then it is evaporated under reduced pressure obtained polysiloxane prepolymers；Second step：It is passed through nitrogen, by polysiloxane pre polymers obtained
Object is warming up to 100~125 DEG C, and the acrylic ester monomer and initiator of the component are added under the temperature condition, is total to
Poly- reaction, reaction terminate to can be prepared by extra-weather-proof Silicone modified acryl's resin.
Chinese patent literature CN106916263A (application number 201710229840.9) also discloses that a kind of organic-silicon-modified
The method of automobile coating water-based acrylic resin, includes the following steps.Step 1：The preparation of sol solution：By 0.5~1 weight
The ethyl orthosilicate of part and the hydrophobic silane of 1.5~2 parts by weight are added in the absolute ethyl alcohol of 35~45 parts by weight, are warming up to
50 DEG C, and it is stirred to react 3h, the anion emulsifier of 3~4 parts by weight is added, continues stirring until material is completely dissolved；Step
Rapid 2：The preparation of single phase：By the butyl methacrylate of 10~15 parts by weight, the styrene of 3~5 parts by weight, 5~10 weight
Part vinyl trimethoxy siloxanes, the acrylic acid of 10~15 parts by weight, the hydroxyethyl methacrylate of 10~15 parts by weight, 5
The vinyl pyrrolidone of~10 parts by weight, 2~5 parts by weight tetramethyl divinyl disiloxanes, 1~3 parts by weight anion
Emulsifier, 0.5~0.8 parts by weight initiator be uniformly mixed obtain single phase；Step 3：Sol solution is placed in reaction vessel
In, pressure control enters single phase dropwise addition in reaction system in 2~4MPa, and time for adding is 1~2h, reaction temperature control
System is at 55~65 DEG C；Step 4：The pH value of the mixture system obtained by pH adjusting agent regulating step 3 is 6~7.
Invention content
Technical problem to be solved by the invention is to provide a kind of organic siloxane modified automobile coating thermoplastic acrylics
The method of resin, the reaction conversion rate is high, and product wear-resisting and waterproof is had excellent performance.
It realizes that the technical solution of the object of the invention is a kind of preparation method of automobile coating thermoplastic acrylic resin, first will
Double bond containing organosiloxane monomer is copolymerized with acrylic monomers in the presence of initiator, then copolymerization product and low surface
The hydrophobic compound of power is compound, obtains organic siloxane modified thermoplastic acrylic resin.
Preparation method specifically includes following steps：
1. in the container with stirring, input solvent starts as bottom material and stirs and be warming up to 100 DEG C~140 DEG C.
2. the mixture of the organosiloxane monomer containing double bond, acrylic monomers, styrene, initiator is added dropwise, 2~
It is dripped off in 4 hours, 0.8~1.5h of isothermal reaction.
3. adding the mixture of initiator and solvent, 0.8~1.5h of heat preservation is finished；The mixed of initiator and solvent is added in repetition
The operation 1~2 time for closing object and isothermal reaction, adds finish for the last time, keep the temperature 3~5h.
4. reaction, which finishes, is cooled to 60 DEG C hereinafter, the hydrophobic compound of low surface tension is added, stir evenly, cooling,
The thermoplastic acrylic resin is obtained after filtering, discharging.
The double bond containing organosiloxane monomer is vinyltriethoxysilane, methacryloxypropyl front three
One or more kinds of compositions in oxysilane or eight methylene cyclotetrasiloxanes.
The acrylic monomers is esters of acrylic acid, methyl acrylic ester, diacrylate esters, acrylic acid, acetic acid second
Alkene or diisocyanate monomer and two or more the composition in the closing addition product of monohydroxy acrylate.
The initiator is one kind in peroxidized t-butyl perbenzoate, benzoyl peroxide.
The hydrophobic compound of the low surface tension is the organosiloxane with polar functional group.
The mass fraction of each reactant added into reactor is as follows：0.1~5 part of organosiloxane monomer, acrylic acid
5~15 parts of monomer, 35~50 parts of styrene.
The dosage of initiator is the 0.5%~4.0% of unsaturated monomer gross mass.
The preparation method of diacrylate performed polymer is by hydroxypropyl acrylate and diisocyanate by hydroxyl and isocyanic acid
Ester molar ratio 1:1 mixing is added organotin as catalyst, is stirred to react at normal temperatures, obtains diacrylate performed polymer and wait for
With.
Automobile coating thermoplastic acrylic resin made from a kind of method produced above.
The present invention has the effect of positive：（1）Acrylic resin molecular weight prepared by the present invention is big, and resin viscosity is big, phase
Than having better wear-resisting and water resistance after common thermoplastic acrylic resin, film forming.（2）Thermoplastic prepared by the present invention
Property acrylic resin, due to the presence of compound low surface tension chain link, smooth performance is able to larger raising, has better
Rapid draing, suitable for the application of vehicle chassis.（3）The preparation method reaction conversion rate of the present invention is high, simple for process.
Specific implementation mode
（Embodiment 1）
The preparation method of automobile coating thermoplastic acrylic resin of the present invention is：First by double bond containing organosiloxane monomer with
Acrylic monomers is copolymerized in the presence of initiator, then compound with the hydrophobic compound of low surface tension, obtains organosilicon
Siloxane modified thermoplastic acrylic resin.
It is as follows：In the container with stirring, suitable solvent is put into as bottom material, is started and is stirred and be warming up to
100 DEG C~140 DEG C；The organosiloxane monomer containing double bond and acrylic monomers, the mixture of styrene, initiator is added dropwise,
It is dripped off in 2~4 hours, isothermal reaction is for a period of time；The mixture for adding initiator and solvent continues heat preservation a period of time；
The operation 1~2 time of the mixture of initiator and solvent and isothermal reaction is added in repetition；Reaction, which finishes, is cooled to 60 ± 10 DEG C, adds
The hydrophobic compound for entering low surface tension, stirs evenly, and the thermoplastic acrylic is obtained after cooling, filtering, discharging
Resin.
Wherein, the solvent is dimethylbenzene.
The double bond containing organosiloxane monomer is vinyltriethoxysilane, methacryloxypropyl front three
One or more kinds of compositions in oxysilane or eight methylene cyclotetrasiloxanes.
The acrylic monomers is esters of acrylic acid, methyl acrylic ester, diacrylate esters, acrylic acid, acetic acid second
Alkene or diisocyanate monomer and two or more the composition in the closing addition product of monohydroxy acrylate.
The initiator is peroxidized t-butyl perbenzoate（TBPB）, benzoyl peroxide（BPO）In one kind.
The hydrophobic compound of the low surface tension is the organosiloxane with polar functional group, such as silane
Oil, BYK310（Bi Ke chemistry）、BYK322（Bi Ke chemistry）、YCK-1070（Firm gram of chemistry）、YCK-1270（Firm gram of chemistry）Deng.
The preparation method of the automobile coating thermoplastic acrylic resin of the present embodiment includes the following steps：
1. weighing 34 parts of dimethylbenzene as dispersion solvent, it is added in reactor, stirring is warming up to 132 DEG C of reflux temperature.
2. weighing vinyltriethoxysilane（The A-151 of union carbide corporation of the U.S.）1 part, 7 parts of butyl methacrylate, first
3 parts of base methyl acrylate, 1 part of acrylic acid, 1 part of diacrylate performed polymer, 39 parts of styrene, peroxidized t-butyl perbenzoate
（TBPB）0.7 part；Above-mentioned material is uniformly mixed, is stirring under reflux temperature, these mixtures is slowly dropped into reactor,
Time for adding 3.0h continues 0.8~1.5h of isothermal reaction after completion of dropwise addition（It is 1h in the present embodiment）, reaction temperature, which controls, to exist
130℃。
The preparation method of wherein diacrylate performed polymer is specific as follows：Weigh 77g（0.59mol）Hydroxypropyl acrylate with
100g hexamethylene diisocyanates（HDI, 0.59mol）, by hydroxyl and isocyanates molar ratio 1:1 mixing, 1.2g, which is added, to be had
Machine tin is stirred to react 30min at normal temperatures as catalyst, obtains diacrylate performed polymer.
3. 2. step after isothermal reaction, 8 parts of xylene solvents and 0.15 part of peroxidating is slowly added dropwise into reactor
T-butyl perbenzoate（TBPB）, time for adding 0.5h, after completion of dropwise addition at 130 DEG C 0.8~1.5h of isothermal reaction（The present embodiment
In be 1h）.
After the completion of adding the reaction of initiator for the first time, be slowly added dropwise again into reactor 8 parts of xylene solvents and
0.15 part of peroxidized t-butyl perbenzoate（TBPB）, time for adding 0.6h, the continuation isothermal reaction 3 at 130 DEG C after completion of dropwise addition
~5h（4h）, reaction finishes.
4. step takes cooling measure after the completion of 3. reacting, the temperature of charge after reaction is made to be down to 60 DEG C hereinafter, filtering, going out
Material；0.5 part of hydrogenation silicone oil is added thereto and stirs evenly, thermoplastic acrylic resin is made in cooling, filtering.
（Embodiment 2）
Remaining is same as Example 1 for the preparation method of the thermoplastic acrylic resin of the present embodiment, the difference is that：
Step 2. in weigh 1 part of eight methylene cyclotetrasiloxane, 6 parts of butyl methacrylate, 3 parts of methyl methacrylate, third
1 part of olefin(e) acid, 40 parts of styrene, peroxidized t-butyl perbenzoate（TBPB）0.7 part；Previous materials are slowly dropped into instead after mixing
Answer device, time for adding 3.1h.
Step 3. in, each dimethylbenzene and peroxidized t-butyl perbenzoate added（TBPB）Time for adding be 0.6h,
The isothermal reaction at 132 DEG C after completion of dropwise addition.
Step 4. in, the hydrophobic compound of the low surface tension of addition is 0.6 part of BYK322（Bi Ke chemistry）.
（Embodiment 3）
Remaining is same as Example 1 for the preparation method of the thermoplastic acrylic resin of the present embodiment, the difference is that：
Step 2. in weigh 1 part of vinyltriethoxysilane, 5 parts of butyl acrylate, 3.5 parts of methyl methacrylate, propylene
0.5 part of acid, 1 part of diacrylate performed polymer, 41 parts of styrene, peroxidized t-butyl perbenzoate（TBPB）0.7 part；Previous materials
Be slowly dropped into reactor after mixing, time for adding 3.2h, after completion of dropwise addition at 133 DEG C isothermal reaction 1h.
The preparation method of the diacrylate performed polymer wherein used is specific as follows：Weigh 37g（0.29mol）Acrylic acid hydroxyl
Propyl ester and 50gTDI（0.29mol）, by hydroxyl and isocyanates mole ratio 1:1.1g organotins are added as catalysis in 1 mixing
Agent is stirred to react 35min at normal temperatures, obtains diacrylate performed polymer, stand for standby use.
Step 3. in, each dimethylbenzene and peroxidized t-butyl perbenzoate added（TBPB）At 133 DEG C after completion of dropwise addition
Lower isothermal reaction.
Step 4. in, the hydrophobic compound of the low surface tension of addition is 0.8 part of YCK-1070（Firm gram of chemistry）.
（Embodiment 4）
Remaining is same as Example 1 for the preparation method of the thermoplastic acrylic resin of the present embodiment, the difference is that：
Step 2. in weigh 1.3 parts of methacryloxypropyl trimethoxy silane, 4 parts of butyl acrylate, methacrylic acid
2.5 parts of methyl esters, 0.5 part of acrylic acid, 1.5 parts of diacrylate performed polymer, 43 parts of styrene, peroxidized t-butyl perbenzoate
（TBPB）0.7 part；Previous materials are slowly dropped into reactor, time for adding 3.1h, after completion of dropwise addition at 135 DEG C after mixing
Isothermal reaction 1h.
The preparation method of the diacrylate performed polymer wherein used is specific as follows：Weigh 26g（0.29mol）Acrylic acid hydroxyl
Propyl ester and 50g isophorone diisocyanate（IPDI, 0.22mol）, 1.5g organotins are added as catalyst, stir at normal temperatures
Reaction 32min is mixed, diacrylate performed polymer, stand for standby use are obtained.
Step 3. in, each dimethylbenzene and peroxidized t-butyl perbenzoate added（TBPB）At 135 DEG C after completion of dropwise addition
Lower isothermal reaction.
Step 4. in, the hydrophobic compound of the low surface tension of addition is 0.4 part of YCK-1070（Firm gram of chemistry）.
（Embodiment 5）
Remaining is same as Example 1 for the preparation method of the thermoplastic acrylic resin of the present embodiment, the difference is that：
Step 2. in weigh 1.5 parts of methacryloxypropyl trimethoxy silane, 2 parts of butyl acrylate, methacrylic acid
2 parts of methyl esters, 1 part of acrylic acid, 0.9 part of diacrylate performed polymer, 45 parts of styrene, benzoyl peroxide（BPO）0.7 part；Before
State material and be slowly dropped into reactor after mixing, time for adding 3.1h, after completion of dropwise addition at 134 DEG C isothermal reaction 1h.
Step 3. in, each xylene solvent and benzoyl peroxide added（BPO, 0.15 part）After completion of dropwise addition
Isothermal reaction at 134 DEG C.
Step 4. in, the hydrophobic compound of the low surface tension of addition is 0.7 part of YCK-1070（Firm gram of chemistry）.
Above-described embodiment prepares the reaction conversion ratio of the thermoplastic acrylic resin, viscosity of thermoplastic acrylic resin, resistance to
Mill, water resistance testing result see the table below 1.
Viscosity is detected according to GB/T 1723.
Wear-resisting property is detected according to GB/T 1768-2006.
Water resistance is according to ISO 2812-2：2007 are detected.
Table 1
It is wear-resisting after film forming, water resistance is preferable by above-mentioned testing result it is found that the molecular resin amount for preparing of the present invention is big.
It should be noted that the foregoing is merely several preferred embodiments of the present invention, it is not limited to this
Invention, although invention is explained in detail with reference to aforementioned embodiments, for those skilled in the art,
Still can modify to the technical solution recorded in aforementioned each embodiment, or which part technical characteristic is carried out etc.
With replacement.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection domain of invention.
Claims (10)
1. a kind of preparation method of automobile coating thermoplastic acrylic resin, it is characterised in that：First by double bond containing organic silica
Alkane monomer is copolymerized with acrylic monomers in the presence of initiator, then the hydrophobic compound of copolymerization product and low surface tension
It is compound, obtain organic siloxane modified thermoplastic acrylic resin.
2. the preparation method of automobile coating thermoplastic acrylic resin according to claim 1, it is characterised in that including with
Lower step：
1. in the container with stirring, input solvent starts as bottom material and stirs and be warming up to 100 DEG C~140 DEG C；
2. the mixture of the organosiloxane monomer containing double bond, acrylic monomers, styrene, initiator is added dropwise, it is small 2~4
When it is interior drip off, 0.8~1.5h of isothermal reaction；
3. adding the mixture of initiator and solvent, 0.8~1.5h of heat preservation is finished；The mixture of initiator and solvent is added in repetition
And the operation of isothermal reaction 1~2 time, it adds finish for the last time, keep the temperature 3~5h；
4. reaction, which finishes, is cooled to 60 DEG C hereinafter, the hydrophobic compound of low surface tension is added, stir evenly, cooling, filtering,
The thermoplastic acrylic resin is obtained after discharging.
3. the preparation method of automobile coating thermoplastic acrylic resin according to claim 1 or 2, it is characterised in that：Institute
State double bond containing organosiloxane monomer be vinyltriethoxysilane, methacryloxypropyl trimethoxy silane or
One or more kinds of compositions in eight methylene cyclotetrasiloxanes.
4. the preparation method of automobile coating thermoplastic acrylic resin according to claim 1 or 2, it is characterised in that：Institute
It is esters of acrylic acid, methyl acrylic ester, diacrylate esters, acrylic acid, vinyl acetate or two isocyanides to state acrylic monomers
Acid ester monomer and two or more the composition in the closing addition product of monohydroxy acrylate.
5. the preparation method of automobile coating thermoplastic acrylic resin according to claim 1 or 2, it is characterised in that：Institute
The initiator stated is one kind in peroxidized t-butyl perbenzoate, benzoyl peroxide.
6. the preparation method of automobile coating thermoplastic acrylic resin according to claim 1 or 2, it is characterised in that：Institute
The hydrophobic compound for the low surface tension stated is the organosiloxane with polar functional group.
7. the preparation method of automobile coating thermoplastic acrylic resin according to claim 2, it is characterised in that reaction
The mass fraction of each reactant added in device is as follows：0.1~5 part of organosiloxane monomer, 5~15 parts of acrylic monomers, benzene
35~50 parts of ethylene.
8. the preparation method of automobile coating thermoplastic acrylic resin according to claim 7, it is characterised in that：Initiator
Dosage be unsaturated monomer gross mass 0.5%~4.0%.
9. the preparation method of automobile coating thermoplastic acrylic resin according to claim 4, it is characterised in that：Two propylene
The preparation method of acid esters performed polymer is by hydroxypropyl acrylate and diisocyanate by hydroxyl and isocyanates molar ratio 1:1 is mixed
It closes, organotin is added as catalyst, is stirred to react at normal temperatures, it is for use to obtain diacrylate performed polymer.
10. automobile coating thermoplastic acrylic resin made from a kind of preparation method as claimed in claim 1.
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| CN110590986A (en) * | 2019-08-27 | 2019-12-20 | 亿美(新丰)实业有限公司 | Modified acrylic resin for automobile paint, preparation method and automobile primer-topcoat paint |
| CN115521679A (en) * | 2022-08-29 | 2022-12-27 | 广东美涂士建材股份有限公司 | Non-top-coat silicone-acrylic self-cleaning stone-like paint and preparation process thereof |
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| CN110590986A (en) * | 2019-08-27 | 2019-12-20 | 亿美(新丰)实业有限公司 | Modified acrylic resin for automobile paint, preparation method and automobile primer-topcoat paint |
| CN110590986B (en) * | 2019-08-27 | 2021-08-10 | 亿美(新丰)实业有限公司 | Modified acrylic resin for automobile paint, preparation method and automobile primer-topcoat paint |
| CN115521679A (en) * | 2022-08-29 | 2022-12-27 | 广东美涂士建材股份有限公司 | Non-top-coat silicone-acrylic self-cleaning stone-like paint and preparation process thereof |
| CN115521679B (en) * | 2022-08-29 | 2024-04-12 | 广东美涂士建材股份有限公司 | Finishing-free silicone-acrylic self-cleaning real stone paint and preparation process thereof |
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Application publication date: 20181016 |