CN104726019A - Isocyanate modified organic silicon resin composition and preparation method and application thereof - Google Patents
Isocyanate modified organic silicon resin composition and preparation method and application thereof Download PDFInfo
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- CN104726019A CN104726019A CN201510164274.9A CN201510164274A CN104726019A CN 104726019 A CN104726019 A CN 104726019A CN 201510164274 A CN201510164274 A CN 201510164274A CN 104726019 A CN104726019 A CN 104726019A
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- polyisocyanates
- resin composition
- isocyanate
- catalyzer
- nco
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- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract 3
- 239000012948 isocyanate Substances 0.000 title abstract 3
- 150000002513 isocyanates Chemical class 0.000 title abstract 3
- 229910052710 silicon Inorganic materials 0.000 title abstract 3
- 239000010703 silicon Substances 0.000 title abstract 3
- 239000007787 solid Substances 0.000 claims abstract description 14
- 230000003287 optical effect Effects 0.000 claims abstract description 11
- 239000004033 plastic Substances 0.000 claims abstract description 11
- 229920003023 plastic Polymers 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000005056 polyisocyanate Substances 0.000 claims description 19
- 229920001228 polyisocyanate Polymers 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 125000005401 siloxanyl group Chemical group 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- -1 acryloxy Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002329 infrared spectrum Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 150000001621 bismuth Chemical class 0.000 claims description 4
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000003983 crown ethers Chemical class 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 150000001261 hydroxy acids Chemical group 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- FDYWJVHETVDSRA-UHFFFAOYSA-N 1,1-diisocyanatobutane Chemical compound CCCC(N=C=O)N=C=O FDYWJVHETVDSRA-UHFFFAOYSA-N 0.000 description 1
- VKLNMSFSTCXMSB-UHFFFAOYSA-N 1,1-diisocyanatopentane Chemical compound CCCCC(N=C=O)N=C=O VKLNMSFSTCXMSB-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- HWXBTNAVRSUOJR-UHFFFAOYSA-N 2-hydroxyglutaric acid Chemical compound OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- ZLDNZVKBVVPZNI-UHFFFAOYSA-N [Zn].CC(C(C(=O)O)(C)C)(CCCC(=O)O)C Chemical compound [Zn].CC(C(C(=O)O)(C)C)(CCCC(=O)O)C ZLDNZVKBVVPZNI-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 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 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses isocyanate modified organic silicon resin composition and a preparation method and application thereof. The obtained isocyanate modified organic silicon resin composition contains more than 60% of solids and is used for hardening and resisting scratches of the surface of optical plastics, and surface hardness and scratch resistance of the optical plastics are improved.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to a kind of isocyanate-modified organosilicon resin composition and its preparation method and application.
Background technology
Optical plastics have density little, be easy to the advantages such as forming process, but hardness is low, easily scratches, and be greatly limit use range.In optical plastics surface-coated one deck stiffened scratch resistance coating, can effectively address this problem.Between 20-40%, there is a large amount of solvents in the general solid content of current use stiffened scratch resistance silicone resin coating material, gives transport and use to bring very large inconvenience, and in use, also bring the pollution of safety factor and VOC.
Summary of the invention
The object of the present invention is to provide a kind of isocyanate-modified organosilicon resin composition and its preparation method and application, the solid content of obtained isocyanate-modified organosilicon resin composition is more than 60%, for the stiffened scratch resistance process on optical plastics surface, surface hardness and the adhesion strength of optical plastics significantly can be improved.
For achieving the above object, the present invention adopts following technical scheme:
A kind of solid content of isocyanate-modified organosilicon resin composition is more than 60%.
Preparation method comprises the following steps:
(1) polyisocyanates, monohydroxy polyprotonic acid, the material being used for blocked isocyanate functional group, toluene and catalysts are mixed, react more than 5 hours at 100-110 DEG C, detect without NCO absorption peak to infrared spectrum;
(2) 25-30 DEG C is cooled to, add siloxanyl monomers, phase-transfer catalyst and deionized water, 2-36 hour is reacted at 5-50 DEG C, underpressure distillation at 55-60 DEG C, sampling is when to test solid content at 180 DEG C be more than 60%, stop underpressure distillation, add urethane cures catalyzer and flow agent, stirring and evenly mixing.
Monohydroxy polyprotonic acid, be 40-55:50-65:100 for the material of blocked isocyanate functional group and the mol ratio of NCO functional group, the weight ratio of toluene, catalysts and polyisocyanates is 10-20:0.001-0.01:1; The weight ratio of siloxanyl monomers, phase-transfer catalyst and polyisocyanates is 1:0.005-0.05:0.125-0.25, the mol ratio of siloxanyl monomers and deionized water is 1:3-8, and the weight ratio of urethane cures catalyzer, flow agent and polyisocyanates is 0.01-5:0.1-1:100.
Described polyisocyanates is vulcabond or triisocyanate, or by polyisocyanates that the isocyanate groups of vulcabond, triisocyanate itself is obtained by reacting; Described monohydroxy polyprotonic acid is the organism containing at least 2 hydroxy-acid groups and an oh group in molecular formula, and total carbon number that contains is less than 10.
The described material for blocked isocyanate functional group, for can react with NCO, makes it at room temperature not have reactive behavior, when being heated to 70-150 DEG C, reversible reaction occurring, makes NCO again have the material of reactive behavior.
Described catalysts is zinc class, tin class or bismuth class catalyzer.
The molecular formula of described siloxanyl monomers is (R
0)
x-Si (OR
1)
(4-X), X=0,1,2,3, R
0for methyl, ethyl, containing epoxy group(ing), containing thiazolinyl, containing acryloxy, containing the one in sulfydryl, amido, R
1for methyl, ethyl or propyl group.
Described phase-transfer catalyst is the one in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
Described urethane cures catalyzer is the one in triethylene diamine, N, N-dimethylcyclohexylamine, dimethyl benzylamine, N, N'-lupetazin, open-chain crown ether, 2,4,6-tri-(dimethylamino methyl) phenol; Described flow agent is silicone based or acrylic acid or the like flow agent.
Described isocyanate-modified organosilicon resin composition is used for the stiffened scratch resistance process on optical plastics surface.
Remarkable advantage of the present invention is: the solid content of obtained isocyanate-modified organosilicon resin composition, more than 60%, for the stiffened scratch resistance process on optical plastics surface, significantly can improve surface hardness and the adhesion strength of optical plastics.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of embodiment 1.
Embodiment
A kind of solid content of isocyanate-modified organosilicon resin composition is more than 60%.
Preparation method comprises the following steps:
(1) polyisocyanates, monohydroxy polyprotonic acid, the material being used for blocked isocyanate functional group, toluene and catalysts are mixed, react more than 5 hours at 100-110 DEG C, detect without NCO absorption peak to infrared spectrum;
(2) 25-30 DEG C is cooled to, add siloxanyl monomers, phase-transfer catalyst and deionized water, 2-36 hour is reacted at 5-50 DEG C, underpressure distillation at 55-60 DEG C, sampling is when to test solid content at 180 DEG C be more than 60%, stop underpressure distillation, add urethane cures catalyzer and flow agent, stirring and evenly mixing.
Monohydroxy polyprotonic acid, be 40-55:50-65:100 for the material of blocked isocyanate functional group and the mol ratio of NCO functional group, the weight ratio of toluene, catalysts and polyisocyanates is 10-20:0.001-0.01:1; The weight ratio of siloxanyl monomers, phase-transfer catalyst and polyisocyanates is 1:0.005-0.05:0.125-0.25, the mol ratio of siloxanyl monomers and deionized water is 1:3-8, and the weight ratio of urethane cures catalyzer, flow agent and polyisocyanates is 0.01-5:0.1-1:100.
Described polyisocyanates is vulcabond or triisocyanate, as butane diisocyanate, pentane diisocyanate, hexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, triphenylmethane triisocyanate etc., or pass through vulcabond, the polyisocyanates that the isocyanate groups of triisocyanate itself is obtained by reacting, as carbodiimide compound, isocyanurate compound etc., common commercial goods is as Bayer Bitterfeld GmbH Desmodur N75, N3390, Mitsui chemical curing agent M-432T, D-208T, the trimer curing agent HXR of NPU company of Japan.
Described monohydroxy polyprotonic acid is the organism containing at least 2 hydroxy-acid groups and an oh group in molecular formula, and total carbon number that contains is less than 10, as tartronic acid, hydroxy-butanedioic acid, hydroxyl pentanedioic acid, Hydroxy M Phthalic Acid, citric acid etc.
The described material for blocked isocyanate functional group is for can react with NCO, it is made at room temperature not have reactive behavior, when being heated to 70-150 DEG C, there is reversible reaction, make NCO again have the material of reactive behavior, comprise phenols, lactams, oximes, beta-dicarbonyl compound, imidazoles, pyrazoles etc., as Resorcinol, ε-caprolactam, Diacetylmonoxime, diethyl malonate, 1,2,4-triazole, 3，5-dimethylpyrazole etc.
Described catalysts is zinc class, tin class or bismuth class catalyzer, as zinc acetylacetonate, tetramethyl-pimelic acid zinc, zinc salicylate, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, 2 ethyl hexanoic acid bismuth, bismuth acetate etc., preferred bismuth class and zinc class catalyzer.
The molecular formula of described siloxanyl monomers is (R
0)
x-Si (OR
1)
(4-X), X=0,1,2,3, R
0for methyl, ethyl, containing epoxy group(ing), containing thiazolinyl, containing acryloxy, containing the one in sulfydryl, amido, R
1for methyl, ethyl or propyl group.
Described phase-transfer catalyst is the one in benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
Described urethane cures catalyzer is the one in triethylene diamine, N, N-dimethylcyclohexylamine, dimethyl benzylamine, N, N'-lupetazin, open-chain crown ether, 2,4,6-tri-(dimethylamino methyl) phenol.
Described flow agent is silicone based or acrylic acid or the like flow agent, as German Bi Ke chemistry BYK 330, BYK358, and enlightening height glide 450, glide 410 etc.
Described isocyanate-modified organosilicon resin composition is used for the stiffened scratch resistance process on optical plastics surface.
Embodiment 1:
Get the Bayer Bitterfeld GmbH N3390(NCO% ≈ 19.6% of 100g) polyisocyanates, the oxysuccinic acid (hydroxy-butanedioic acid) of 25g, the Diacetylmonoxime of 24.5g, 1500g toluene and 0.2g bismuth acetate, after stirring, start to be heated to 105 DEG C, continue reaction 5 hours, infrared spectrum detection is carried out in sampling, as found out at 2270cm in Fig. 1, figure
-1neighbouring NCO absorption peak disappears.When being cooled to 25 DEG C, add Union carbide A-162 500g, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane 50g, 4-butyl ammonium hydrogen sulfate 5g and deionized water 300g, stir lower maintenance liquid temperature to react 24 hours at 25 DEG C, underpressure distillation afterwards, liquid temperature remains on 50 DEG C, and in still, absolute pressure is 100kPa.After 8 hours, sample thief dries 1 hour in 180 DEG C of baking ovens, and test solid content, as table 1, solid content is 66%.Stop underpressure distillation, add 1g open-chain crown ether and 0.5g BYK358 flow agent, continue stirring 20 minutes, be designated as A liquid.
In envrionment temperature 20 DEG C, humidity 55% time, on polycarbonate (PC) sheet material, apply prepared A liquid, after top coat levelling, put into baking box, toast 3 hours at 120 DEG C.Carry out Performance Detection after taking out cooling, as shown in table 2 contrasts, the obtained isocyanate-modified organosilicon resin composition of high solids content significantly improves surface hardness and the adhesion strength of PC.
Table 1 solid content test result
PC performance comparison before and after table 2 stiffened
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. an isocyanate-modified organosilicon resin composition, is characterized in that: solid content is more than 60%.
2. prepare a method for isocyanate-modified organosilicon resin composition as claimed in claim 1, it is characterized in that: comprise the following steps:
Polyisocyanates, monohydroxy polyprotonic acid, the material being used for blocked isocyanate functional group, toluene and catalysts are mixed, reacts more than 5 hours at 100-110 DEG C, detect without NCO absorption peak to infrared spectrum;
Be cooled to 25-30 DEG C, add siloxanyl monomers, phase-transfer catalyst and deionized water, 2-36 hour is reacted at 5-50 DEG C, underpressure distillation at 55-60 DEG C, sampling is when to test solid content at 180 DEG C be more than 60%, stop underpressure distillation, add urethane cures catalyzer and flow agent, stirring and evenly mixing.
3. method according to claim 2, it is characterized in that: monohydroxy polyprotonic acid, be 40-55:50-65:100 for the material of blocked isocyanate functional group and the mol ratio of NCO functional group, the weight ratio of toluene, catalysts and polyisocyanates is 10-20:0.001-0.01:1; The weight ratio of siloxanyl monomers, phase-transfer catalyst and polyisocyanates is 1:0.005-0.05:0.125-0.25, the mol ratio of siloxanyl monomers and deionized water is 1:3-8, and the weight ratio of urethane cures catalyzer, flow agent and polyisocyanates is 0.01-5:0.1-1:100.
4. method according to claim 2, is characterized in that: described polyisocyanates is vulcabond or triisocyanate, or by polyisocyanates that the isocyanate groups of vulcabond, triisocyanate itself is obtained by reacting; Described monohydroxy polyprotonic acid is the organism containing at least 2 hydroxy-acid groups and an oh group in molecular formula, and total carbon number that contains is less than 10.
5. method according to claim 2, it is characterized in that: the described material for blocked isocyanate functional group, for can react with NCO, makes it at room temperature not have reactive behavior, when being heated to 70-150 DEG C, there is reversible reaction, make NCO again have the material of reactive behavior.
6. method according to claim 2, is characterized in that: described catalysts is zinc class, tin class or bismuth class catalyzer.
7. method according to claim 2, is characterized in that: the molecular formula of described siloxanyl monomers is (R
0)
x-Si (OR
1)
(4-X), X=0,1,2,3, R
0for methyl, ethyl, containing epoxy group(ing), containing thiazolinyl, containing acryloxy, containing the one in sulfydryl, amido, R
1for methyl, ethyl or propyl group.
8. method according to claim 2, is characterized in that: described phase-transfer catalyst is the one in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
9. method according to claim 2, it is characterized in that: described urethane cures catalyzer is triethylene diamine, N, N-dimethylcyclohexylamine, dimethyl benzylamine, N, N'-lupetazin, open-chain crown ether, 2, one in 4,6-tri-(dimethylamino methyl) phenol; Described flow agent is silicone based or acrylic acid or the like flow agent.
10. an application for isocyanate-modified organosilicon resin composition as claimed in claim 1, is characterized in that: described isocyanate-modified organosilicon resin composition is used for the stiffened scratch resistance process on optical plastics surface.
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|---|---|---|---|---|
| US6610777B1 (en) * | 1999-07-30 | 2003-08-26 | Ppg Industries Ohio, Inc. | Flexible coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| CN101679598A (en) * | 2007-04-27 | 2010-03-24 | 纳米X有限公司 | Method for the production of a coating material |
| CN102070987A (en) * | 2009-11-23 | 2011-05-25 | 比亚迪股份有限公司 | Coating and optical element |
| CN104231914A (en) * | 2014-09-16 | 2014-12-24 | 上海应用技术学院 | Optical plastic protection coating and preparation method thereof |
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|---|---|---|---|---|
| US6610777B1 (en) * | 1999-07-30 | 2003-08-26 | Ppg Industries Ohio, Inc. | Flexible coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| CN101679598A (en) * | 2007-04-27 | 2010-03-24 | 纳米X有限公司 | Method for the production of a coating material |
| CN102070987A (en) * | 2009-11-23 | 2011-05-25 | 比亚迪股份有限公司 | Coating and optical element |
| CN104231914A (en) * | 2014-09-16 | 2014-12-24 | 上海应用技术学院 | Optical plastic protection coating and preparation method thereof |
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