CN102731558A - Organosilicone oligomer and preparation method thereof, and bi-component system and application thereof - Google Patents
Organosilicone oligomer and preparation method thereof, and bi-component system and application thereof Download PDFInfo
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- CN102731558A CN102731558A CN2012101884320A CN201210188432A CN102731558A CN 102731558 A CN102731558 A CN 102731558A CN 2012101884320 A CN2012101884320 A CN 2012101884320A CN 201210188432 A CN201210188432 A CN 201210188432A CN 102731558 A CN102731558 A CN 102731558A
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Abstract
The invention provides an organosilicone oligomer and a preparation method thereof. The organosilicone oligomer has a general formula of (R1R2R3SiO1 / 2) a (R4R5SiO) b (R6SiO3 / 2) c (SiO2) d. R1, R2 and R3 represent methyl or ethyl; R4, R5 and R6 represent vinyl or C1-16 alkyl, or C1-6 cycloalkyl, or aryl, or C1-18 fluoroalkyl or groups shown as below; and a, b, c and d satisfy the relations of: a+b +c+d=1, 0<= a <= 0.2, 0< b <=1, 0 < c < =1, and 0<=d<= 0.15. The invention also provides a bi-component system containing the organosilicone oligomer and application thereof. The organosilicone oligomer has advantages of excellent function, low viscosity, no solvent and easy operation, and can be used as a resin component of a high solid content bi-component coating system or used as a raw material for the synthesis of modified polysiloxane resin, and is applicable to industrial protective coating with weatherability and corrosion resistance.
Description
Technical field
The invention belongs to the high-molecular coating chemical technology field, be specifically related to a kind of organosilicon oligopolymer and preparation method thereof, also relate to the bicomponent system and the application thereof that comprise this organosilicon oligopolymer.
Background technology
The organosilicon oligopolymer is a kind of very important midbody in the organosilicon industry, and mostly they are can directly be used by the silane preparation, and also further processing and preparing becomes superpolymer such as silicone resin.Because organosilane is of a great variety, therefore, give the numerous alternatives in the design of organosilicon oligomer structure, this is a big characteristic of organosilicon oligopolymer.The hydrolytic condensation of silane mainly is the condensation hydrolysis of the alkoxyl group that links to each other with Siliciumatom, because the alkoxyl group quantity on the Siliciumatom is more, therefore can carry out limited hydrolysis or complete hydrolysis as required.The organosilicon oligopolymer has developed ripely relatively; Transregional company's DOW CORNING, Degussa and watt gram etc. all have the product of a lot of oligopolymer; Like DC-3074, Z-6018, Dynasylan 6498 etc.; But it remains a very potential research field, and academia also is among the upsurge for the research of organosilicon oligopolymer always.
The modification of polymkeric substance is the scientific research focus of current era, and the performance of single polymers has been difficult to satisfy the requirement of actual needs, and ZGK 5 has outstanding weathering resistance high thermal resistance, but its mechanical property is not enough.Therefore, need carry out modification to it, modified method commonly used comprises epoxide modified, acrylic acid modified and polyurethane-modified.The vinylformic acid organosilicon coating is the organic polymer modified polyorganosiloxane coating of the s-generation, has stronger anticorrosion and ability and ultraviolet resistance.
According to bibliographical information, its coating of acroleic acid modified polysiloxane has remarkable weather-proof ageing-resistant performance and ornamental, and in very high uv environment, the vinylformic acid ZGK 5 does not obviously fade, and epoxy polysiloxane has and significantly fades and variable color.The good snappiness that while vinylformic acid ZGK 5 possesses makes it be more suitable for the structure of this long-term vibration of bridge.And epoxy possesses outstanding advantage in some mechanical properties such as hardness.The vinylformic acid polysiloxane coating materials that the epoxy polysiloxane resin that the existing win wound Degussa trade mark is SILIKOPON EF on market at present, the vinylformic acid polysiloxane coating materials that Akzo Nobel's trade mark is interfine979 and the marine rainbow old man trade mark are 55000 C etc.
US6391999B1 has reported a kind of epoxy radicals silicone hydride oligopolymer and preparation process thereof; Be raw material mainly with organoalkoxysilane and epoxy silane; But also mention monomethyl acryloyl-oxy base silane in the patent is that raw material comes the synthesizing organo-silicon oligopolymer, and catalyzer is a Zeo-karb; Though this patent has been included a lot of silane monomer raw materials; But its defective is that the organosilicon oligopolymer viscosity at room temperature for preparing is very big; Even appear solid-state; In ensuing constructing operation, can bring inconvenience like this, (more than 60 ℃) use better in hot environment, and are inapplicable under the following perhaps low temperature of normal temperature.
Summary of the invention
The purpose of this invention is to provide a kind of organosilicon oligopolymer and preparation method thereof; This organosilicon oligopolymer not only has excellent function property; And viscosity is low, and solvent-free existence is easier to operation; It can be used as the resin Composition of two component industrial protection coating systems, also can be used as raw material synthesis modification polyorganosiloxane resin.
The present invention realizes through following technical scheme: a kind of organosilicon oligopolymer, and its general formula is:
(R
1R
2R
3SiO
1/2)
a(R
4R
5SiO)
b(R
6SiO
3/2)
c(SiO
2)
d，
Wherein, R
1, R
2, R
3Be methyl or ethyl; R
4, R
5, R
6Be the alkyl of vinyl or 1-16 carbon atom, or the fluoro-alkyl of the naphthenic base of 1-6 carbon atom, an aryl or 1-18 carbon atom or
,
,
,
A+b+c+d=1, and 0≤a≤0.2,0＜b＜1.0,0＜c＜1.0,0≤d≤0.15.
The viscosity of said organosilicon oligopolymer is 50-2000mPa.s.
A kind of method for preparing above-mentioned organic low silicon polymers, its step comprises:
⑴ be that silane B or a kind of, the mass percent among the C of 0-50% is after the cationic exchange resin of 2-4% mixes and is heated to 20-80 ℃ with mass percent; In said mixture, adding mole number is silane alkoxy groups total moles 0.25-1.0 water doubly, insulation reaction 20-40 minute then;
⑵ add a kind of among silane C that mass percent is 50-100% or the B in the mixture of reaction products of step ⑴; Or the mixture of a kind of and silane D among silane C or the B; Reheat is after 20-80 ℃; In said mixture, adding mole number is silane alkoxy groups total moles 0.3-1.0 water doubly, and insulation reaction 2-4 hour then, underpressure distillation obtained said organosilicon oligopolymer behind the cold filtration;
Said silane B, D are the different organoalkoxysilane of structure, and general structure is: R
8Si (R
c)
n(OR
d)
3-n, R wherein
8Fluoro-alkyl for the alkyl of 1-20 carbon atom, naphthenic base, aryl, methoxyl group, oxyethyl group, a 1-18 carbon atom; R
c, R
dBe the alkyl of 1-4 carbon atom, trimethyl silicon based; N is the integer between the 0-3;
Said silane B; D comprises methyltrimethoxy silane; Union carbide A-162; Dimethyldimethoxysil,ne; Dimethyldiethoxysilane; Propyl trimethoxy silicane; Propyl-triethoxysilicane; R-chloropropyl trimethoxyl silane; Chloropropyl triethoxysilane; Chloropropylmethyldimethoxysilane; The chloropropyl methyldiethoxysilane; Methyl-isobutyl dimethoxy silane; The methyl-isobutyl diethoxy silane; The isobutyl-Trimethoxy silane; The isobutyl-triethoxyl silane; Methyl n-hexyl dimethoxy silane; Methyl n-hexyl diethoxy silane; The n-hexyl Trimethoxy silane; The n-hexyl triethoxyl silane; Methyl Octyl dimethoxy silane; The Methyl Octyl diethoxy silane; The octyl group Trimethoxy silane; Octyltri-ethoxysilane; The dodecyl Trimethoxy silane; The dodecyl triethoxyl silane; The hexadecyl Trimethoxy silane; The hexadecyl triethoxyl silane; The octadecyl Trimethoxy silane; Octadecyltriethoxy silane; Phenyltrimethoxysila,e; Phenyl triethoxysilane; Aminomethyl phenyl dimethoxy silane; The aminomethyl phenyl diethoxy silane; Dimethoxydiphenylsilane; The phenylbenzene diethoxy silane; Cyclohexyl trimethoxy silane; The cyclohexyl triethoxyl silane; Cyclohexyl methyl dimethoxy silane; The cyclohexyl methyl diethoxy silane; Dicyclo amyl group dimethoxy silane; Dicyclo amyl group diethoxy silane; Methyl silicate; Tetraethoxy etc.; Also comprise dimethyl-ring body (D3; D4; D5; D6 etc.); The methyl ethylene ring body; The aminomethyl phenyl ring body; The trimethylammonium methoxy silane; Trimethylethoxysilane; SWS-F 221; Pentamethyl disiloxane; Tetramethyl disiloxane; The trifluoro propyl Trimethoxy silane; The trifluoro propyl triethoxyl silane; Hexafluoro butyl propyl trimethoxy silicane; Ten difluoro heptyl propyl trimethoxy silicanes; Ten difluoro heptyl propyl group methyl dimethoxysilanes; 13 fluoro octyltri-ethoxysilane; 13 fluoro octyl group Trimethoxy silanes; 17 fluorine decyl Trimethoxy silanes; 17 fluorine decyl triethoxyl silanes etc.
The structure of said silane C does
,
,
Or
, R wherein
a, R
bBe the alkyl of 1-4 carbon atom, trimethyl silicon based; R
7Be methyl or H; M is the integer between the 0-3.
Said silane C comprises 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, methacryloxy methyltrimethoxy silane, methacryloxy Union carbide A-162, methacryloxy methyl dimethoxy silane, methacryloxy methyl diethoxy silane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl trimethylsiloxy group silane.
The ionic exchange resin of the Rhom and Hass that cationic exchange resin adopts, like Amberrlite IR-120Na, Amberrlite IRP-69.
Underpressure distillation is at pressure 10mmHg-20mmHg among the step ⑵, removes under 20 ℃-80 ℃ the condition that low-boiling-point substance obtains.
Another object of the present invention provides bicomponent system and the application thereof that comprises this organosilicon oligopolymer; Resulting pair of component system of the present invention has good weathering resistance, preservative property; And be used for coating system and good consistency arranged with color stuffing; In configuration during coating system, only need add a small amount of or not solubilizing agent guaranteed that with regard to the configurable good coating systems of various aspects of performance such as leveling characteristics, modest viscosity that obtain coating meets the requirement of environmental protection standard.
A kind of bicomponent system that comprises above-mentioned organosilicon oligopolymer is characterized in that: said bicomponent system is (2-5) by mass ratio: 1 resin Composition and curing agent component are formed; Said resin portion subpackage contains right and requires organosilicon oligopolymer in 1; Also comprise modified organic silicone resin E and contain among the epoxy resin F of two above epoxy group(ing) one or both, wherein modified organic silicone resin E is obtained by oligopolymer that contains methacryloxy in the organosilicon oligopolymer and acrylic ester monomer copolymerization; Said curing agent component is to contain amino silicoorganic compound M, and the structural formula of M does
, R wherein
9Alkyl for 1-4 carbon atom; R
10Alkyl for H, a 1-4 carbon atom; R
11, R
12Alkyl and alkoxyl group for 1-4 carbon atom; O is the integer between the 1-3, and p is the integer between the 1-20.
Said modified organic silicone resin E is to be that the organosilicon oligopolymer that contains methacryloxy of 10-90% and acrylic ester monomer that mass percent is 10-90% obtain through copolymerization under 70-140 ℃ by mass percent.
Said acrylic ester monomer comprises methyl acrylate; TEB 3K; Ethyl propenoate; Jia Jibingxisuanyizhi; Propyl acrylate; Propyl methacrylate; Bing Xisuandingzhi; NSC 20956; NSC 20949; Propenoic acid, 2-methyl, isobutyl ester; Tert-butyl acrylate; The methacrylic tert-butyl acrylate; The vinylformic acid isopentyl ester; The methacrylic isoamyl valerate; Lauryl acrylate; Lauryl methacrylate(LMA); Ethyl acrylate; Methylacrylic acid-2-ethylhexyl; The vinylformic acid dicyclopentenyloxyethyl methacrylate; The methylacrylic acid dicyclopentenyloxyethyl methacrylate; IBOA; Isobornyl methacrylate; Vinylbenzene; Acrylic amide; Vinyl cyanide; Suitable radical initiator comprises Lucidol, 2,4-dichlorobenzoperoxide, isopropyl benzene hydroperoxide, tert-butyl peroxide and Diisopropyl azodicarboxylate.Available solvent is butylacetate, 1-Methoxy-2-propyl acetate, butanone or their mixed solvent.
The solid content of said modified organic silicone resin E is 60-100%, and viscosity is 100-3000mPa.s.
Said epoxy resin F is aliphatics or cycloaliphatic epoxy resin, and epoxy equivalent (weight) has at least two epoxide function bases between 100-500.
Said epoxide comprises product D.E.R. 736, D.E.R. 732, XZ92466, XZ92465, ERL-4221C, the ERL-4221D of DOW Chemical; And the product 3 of the moist pharmaceutical Co. Ltd in Suzhou; 4-epoxycyclohexyl methyl-3,4-epoxycyclohexyl manthanoate (code name S-21), two (7-oxabicyclo [4.1.0] 3-methyl in heptan adipic acid esters), N, N; N; N ,-Fourth Ring oxygen propyl group-4,4-MDA, triglycidyl group PARA AMINOPHENOL, two (3; 4-epoxycyclohexyl methyl)-adipic acid ester (code name S-28), EHPE-3150CE, hexahydrophthalic acid bisglycidyl ester (code name S-182), tetrahydrophthalic acid bisglycidyl ester (code name S-184), 3; 4-epoxycyclohexyl methyl methacrylic acid ester, 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester (S-186), 3; 3'-[oxygen base dimethylene] two [3-ethyl] trimethylene oxide, 3-ethyl-3-propylene oxide methyl alcohol, 4 vinyl epoxy cyclohexane, 1; 4-butanediol diglycidyl ether, NSC 7352 diepoxide, 3,4-epoxy cyclohexane carboxylate methyl ester, 2,2'-[[2; Two [(oxa-cyclo propyl methoxy) methyl]-1 of 2-; The 3-propylidene] two (oxygen methylene radical)] two-oxyethane, 3-(4-glycidyl butoxy)-1,2-Ucar 35, neopentylglycol diglycidyl ether, four glycidyl group-4,4 '-diaminodiphenyl oxide, four glycidyl group-3; 4 '-diaminodiphenyl oxide, 1; Two (N, the N-2-glycidyl aminomethyl) hexanaphthenes of 3-, 3-(4-glycidyl butoxy)-1, the 2-Ucar 35; Code name is that the epoxy resin of S-60, epoxy resin that code name is KIP100 and KIP150 and the code name epoxy resin that is S-31, epoxy resin, the code name that code name is S-500 are the epoxy resin of S-720, and products C ELLO-XIDE 2081, EPOLEAD GT401, CYCLOMER M100, CELLOXIDE 3000, EPOLEAD PB3600, Eternacoll OXBP, Eternacoll OXIPA, Eternacoll OXMA, the Eternacoll EHO of Japanese Daicel company.
In the said bicomponent system, the mass content of organosilicon component is 50-100%, and said organosilicon component comprises the organosilicon oligopolymer, the organosilicon part in acryl-modified silicone resin resin and the solidifying agent.
Solid content is 80-100% in the said bicomponent system.
Another object of the present invention provides the application of above-mentioned pair of component system.
Said bicomponent system is used for the industrial protection coating system.
Organosilicon oligopolymer of the present invention has a plurality of functional groups, has excellent function property, and is of many uses, and viscosity is low, can under normal temperature or low temperature, use.The two component epoxy silicone resin that contains organosilicon oligopolymer according to the invention is multiple cross-linked curing system; The crosslinking curing of existing epoxy-amine is or/and Michael reaction is crosslinked; The crosslinking curing that organosilicon alcoxyl base is also arranged; Can be deployed into different viscosity according to demand, the system of different set times.When resulting pair of component system of the present invention used as coating system and color stuffing good consistency is arranged; When the configuration coating system; Only need add a small amount of or not solubilizing agent with regard to the configurable good coating systems of various aspects of performance such as leveling characteristics, modest viscosity that obtain; This has just guaranteed the VOC content that coating system is lower, environmental protection more, and be applicable to industrial protection coating such as weathering resistance and protection against corrosion.
Embodiment
Further specify the present invention through following specific embodiment.
Embodiment 1
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add methyltrimethoxy silane 150g; Catalyst A mberrlite IR-120Na 18.2g; Stirring also is heated to 50 ℃, drips the water of 20.85g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 120g SWS-F 221 and 330g 3-glycidoxypropyltrime,hoxysilane, when treating that temperature rises to 60 ℃; Drip 36.76g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 10mmHg; Decompression removes low-boiling-point substance under 20 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A1.Record A1 viscosity 200mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.21(s，H
a)，3.55(s，H
b)，0.58(t，H
c)，1.5(m，H
d)，3.37(m，H
e)，3.63(q，H
f)，2.86(t，H
g)，2.63(q，H
h)。
Embodiment 2
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add dimethyldimethoxysil,ne 250g; Catalyst A mberrlite IRP-69 15g; Stirring also is heated to 20 ℃, drips the water of 14.9g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 50g propyl trimethoxy silicane and 200g 3-glycidoxypropyltrime,hoxysilane, when treating that temperature rises to 40 ℃; Drip 96.06g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 30 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A2.Record A2 viscosity 280mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.90(t，H
a)，1.40(q，H
b)，0.58(t，H
c)，3.55(s，H
d)，0.14(s，H
e)，1.50(m，H
f)，3.37(m，H
g)，3.63(q，H
h)，2.86(t，H
i),?2.63(q，H
j)。
Embodiment 3
In the 100mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add dimethyldiethoxysilane 100g; Catalyst A mberrlite IR-120Na 18.3g; Stirring also is heated to 50 ℃, drips the water of 24g, dropwises back insulation reaction 0.5h;
Afterwards, the mixture that adds 110g isobutyl-Trimethoxy silane and 290g 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; When treating that temperature rises to 50 ℃, drip 92.36g water again, dropwise about the insulation reaction 3h of back; Cooling is also filtered; At the highest 20mmHg, decompression removes low-boiling-point substance under 60 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A3 again.Record A3 viscosity 1080mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.91(b，H
a)，1.80(m，H
b)，0.54(t，H
c)，3.55(s，H
d)，0.14(s，H
e)，0.58(t，H
f)，1.50(m，H
g)，1.43(m，H
h)，1.52(m，H
i)，1.70(m，H
j),?2.87(m，H
k),?1.66(m，H
l)。
Embodiment 4
In the 100mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add tetramethoxy-silicane 19.5g; Catalyst A mberrlite IR-120Na 12g; Stirring also is heated to 30 ℃, and the water of Dropwise 5 .5g dropwises back insulation reaction 0.5h;
Afterwards, the mixture that adds 80g n-octyl triethoxyl silane and 270g 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane; When treating that temperature rises to 50 ℃, drip 78.55g water again, dropwise about the insulation reaction 3h of back; Cooling is also filtered; At the highest 10mmHg, decompression removes low-boiling-point substance under 30 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A4 again.Record A4 viscosity 690mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：1.21(t，H
a)，3.83(m，H
b)，3.79(t，H
c)，1.53(m，H
d)，1.43(m，H
e)，1.29(m，H
f)，1.31(m，H
g)，0.88(t，H
h)，3.55(s，H
i)，0.58(t，H
j),?1.30(m，H
k),?1.43(m，H
l)，1.52(m，H
m),?1.70(m，H
n)?，2.87(m，H
o),?1.66(m，H
p)。
Embodiment 5
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add tetraethoxysilane 60g; Catalyst A mberrlite IR-120Na 11.7g; Stirring also is heated to 60 ℃, drips 10.38 water, dropwises back insulation reaction 0.5h;
Afterwards, the mixture that adds 150g dimethyl-diethoxy silane and 300g 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane; When treating that temperature rises to 60 ℃, drip 38.39g water again, dropwise about the insulation reaction 3h of back; Cooling is also filtered; At the highest 10mmHg, decompression removes low-boiling-point substance under 50 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A5 again.Record A5 viscosity 740mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：1.21(t，H
a)，3.83(q，H
b)，0.14(s，H
c)，0.58(t，H
d)，1.30(m，H
e)，1.43(m，H
f)，1.52(m，H
g)，1.70(m，H
h)，2.87(m，H
i)，1.66(m，H
j)。
Embodiment 6
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add dimethyldimethoxysil,ne 55g; Catalyst A mberrlite IRP-69 13.7g; Stirring also is heated to 70 ℃, drips 16.50 water, dropwises back insulation reaction 0.5h;
Afterwards, the mixture that adds 200g phenyltrimethoxysila,e and 200g 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane; When treating that temperature rises to 50 ℃, drip 82.84g water again, dropwise about the insulation reaction 3h of back; Cooling is also filtered; At the highest 10mmHg, decompression removes low-boiling-point substance under 40 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A6 again.Record A6 viscosity 900mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：7.01(t，H
a)，7.28(t，H
b)，6.95(t，H
c)，3.55(s，H
d)，0.14(s，H
e)，1.21(t，H
f)，3.83(q，H
g)，0.58(t，H
h)，1.30(m，H
i)，1.43(m，H
j)?，1.52(m，H
k)，1.70(m，H
l)，2.87(m，H
m)，1.66(m，H
n)。
Embodiment 7
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add aminomethyl phenyl dimethoxy silane 80g; Catalyst A mberrlite IR-120Na 24g; Stirring also is heated to 80 ℃, drips 8.8 water, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 420g vinyltrimethoxy silane and 300g 3-glycidoxy propyl group methyl dimethoxysilane, when treating that temperature rises to 50 ℃; Drip 193.34g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 20mmHg; Decompression removes low-boiling-point substance under 50 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A7.Record A7 viscosity 1550mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：5.17(s，H
a)，5.42(s，H
b)，5.30(s，H
c)，3.55(s，H
d)，0.66(s，H
e)，7.18(t，H
f)，7.27(t，H
g)，7.45(b，H
h)，0.14(s，H
i)，1.02(t，H
j)，1.50(m，H
k)，3.37(m，H
l)?，3.63(t，H
m)，2.86(m，H
n),?2.63(q，H
o)。
Embodiment 8
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add methyl-propyl dimethoxy silane 60g; Catalyst A mberrlite IR-120Na 16.2g; Stirring also is heated to 70 ℃, drips 11.02 water, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 180g phenyl triethoxysilane and 300g 3-glycidoxy propyl group methyldiethoxysilane, when treating that temperature rises to 80 ℃; Drip 48.58g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 20mmHg; Decompression removes low-boiling-point substance under 80 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A8.Record A8 viscosity 2000mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：7.45(t，H
a)，7.27(t，H
b)，7.18(b，H
c)，3.83(q，H
d)，1.21(t，H
e)，1.40(m，H
f)，0.90(t，H
g)，1.02(t，H
h)，0.14(s，H
i)，1.50(m，H
j)?，3.37(q，H
k)，3.63(m，H
l),?2.86(m，H
m)?,?2.63(q，H
n)。
Embodiment 9
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add methyl n-octyl propyl group dimethoxy silane 200g; Catalyst A mberrlite IR-120Na 13.5g; Stirring also is heated to 60 ℃, drips the water of 16.44g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 50g propyl-triethoxysilicane and 200g 3-acryloxy propyl-triethoxysilicane, when treating that temperature rises to 80 ℃; Drip 67.00g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 20mmHg; Decompression removes low-boiling-point substance under 60 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A9.Record A9 viscosity 1900mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.90(t，H
a)，1.40(m，H
b)，0.58(t，H
c)，3.83(q，H
d)，1.21(t，H
e)，1.30(m，H
f)，1.29(t，H
g)，1.31(m，H
h)，0.88(t，H
i)，1.02(t，H
j)?，0.14(s，H
k)，1.60(m，H
l),?4.20(t，H
m)?,6.05(t，H
n)?,?5.80(b，H
o)?,6.43(b，H
p)。
Embodiment 10
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add Union carbide A-162 300g; Catalyst A mberrlite IR-120Na 18g; Stirring also is heated to 40 ℃, drips the water of 39.71g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 30g hexadecyl Trimethoxy silane and 270g 3-glycidoxy propyl group methyl dimethoxysilane, when treating that temperature rises to 60 ℃; Drip 48.10g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 20mmHg; Decompression removes low-boiling-point substance under 60 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A10.Record A10 viscosity 720mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.88(t，H
a)，1.31(m，H
b)，1.29(m，H
c)，1.26(m，H
d)，1.30(m，H
e)，0.58(t，H
f)，3.55(s，H
g)，0.14(s，H
h)，1.02(t，H
i)，1.51(m，H
j)?，3.37(t，H
k)，3.63(m，H
l),?2.86(m，H
m),?2.63(q，H
n),?0.19(s,?H
o),3.83(q，H
p),?1.21(t，H
q)。
Embodiment 11
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add Union carbide A-162 150g; Catalyst A mberrlite IR-120Na 12g; Stirring also is heated to 60 ℃, drips the water of 29.78g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 100g cyclohexyl methyl dimethoxy silane and 150g 3-acryloxy propyl trimethoxy silicane, when treating that temperature rises to 80 ℃; Drip 50.19g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 55 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A11.Record A11 viscosity 1940mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.19(s,?H
a)，3.83(q,?H
b)，1.21(t,?H
c)，0.14(s,?H
d)，1.40(m,?H
e)，1.60(m,?H
f)，1.53(m,?H
g)，1.49(m,?H
h)，3.55(s，H
i)，0.58(t，H
j)?，1.60(m，H
k)，4.20(t,?H
l)，6.05(t，H
m)，5.80(b，H
n)，6.43(b，H
o)。
Embodiment 12
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add 3-methacryloxypropyl trimethoxy silane 150g; Catalyst A mberrlite IR-120Na 13.5g; Stirring also is heated to 20 ℃, drips the water of 29.78g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 180g cyclopentyl-methyl dimethoxy silane and 300g 3-glycidoxy propyl group methyldiethoxysilane, when treating that temperature rises to 50 ℃; Drip 55.45g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 55 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A12.Record A12 viscosity 460mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.19(s,?H
a)，3.79(t,?H
b)，1.77(m,?H
c)，3.37(t,?H
d)，3.63(m,?H
e)，2.86(m,?H
f)，2.63(m,?H
g)，3.83(q,?H
h)，1.21(t，H
i)，0.14(s，H
j)?，1.50(m，H
k)，1.60(m,?H
l)，1.56(m，H
m)，3.55(s，H
n)，0.58(t，H
o)，1.60(m，H
p)，4.20(t,?H
q)，2.01(s，H
r)，5.58(s，H
s)，6.15(s，H
t)。
Embodiment 13
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add the mixture of 200g phenyl methyl dimethoxy silane and 300g 3-methacryloxypropyl dimethoxy silane, catalyst A mberrlite IR-120Na 15g is when treating that temperature rises to 60 ℃; Drip 32.40g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 55 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A13.Record A13 viscosity 110mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：7.45(t,?H
a),?7.27(t,?H
b),?7.18(b,?H
c),?3.55(s,?H
d)，0.66(s,?H
e)，0.14(s,?H
f),?1.02(t,?H
g)，1.60(m,?H
h)，4.20(t,?H
i)，2.01(s,?H
j)，5.58(s,?H
k)，6.15(s,H
l)。
Embodiment 14
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add 3-acryloxy propyl group methyldiethoxysilane 100g; Catalyst A mberrlite IR-120Na 15g; Stirring also is heated to 60 ℃, drips the water of 15.50g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 150g methyltrimethoxy silane and 250g phenyltrimethoxysila,e, when treating that temperature rises to 60 ℃; Drip 70.26g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 10mmHg; Decompression removes low-boiling-point substance under 35 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A14.Record A14 viscosity 590mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：7.45(t,?H
a),?7.27(t,?H
b),?7.18(b,?H
c),?3.55(s,?H
d)，0.14(s,?H
e)，1.02(t,?H
f),?1.60(m,?H
g)，4.20(t,?H
h)，2.01(s,?H
i)，5.58(s,?H
j)，6.15(s,?H
k)，0.19(s,?H
l)。
Embodiment 15
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add the mixture of 200g dimethyldiethoxysilane and 600g 3-methacryloxypropyl triethoxyl silane, catalyst A mberrlite IR-120Na 24g is when treating that temperature rises to 40 ℃; Drip 94.76g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 55 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A15.Record A15 viscosity 300mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.14(s,?H
a),?3.83(q,?H
b),?1.21(t,?H
c),?0.58(t,?H
d)，1.60(m,?H
e),?4.20(t,?H
f)，2.01(s,?H
g)，5.58(s,?H
h)，6.15(s,?H
i)。
Embodiment 16
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add 3-methacryloxypropyl methyldiethoxysilane 100g; Catalyst A mberrlite IR-120Na 15g; Stirring also is heated to 50 ℃, drips the water of 13.80g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 300g Union carbide A-162 and 200g propyl group methyldiethoxysilane, when treating that temperature rises to 50 ℃; Drip 39.59g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 10mmHg; Decompression removes low-boiling-point substance under 40 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A16.Record A16 viscosity 440mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.19(s,?H
a),?3.83(q,?H
b),?1.21(t,?H
c),?0.14(s,?H
d)，1.02(t,?H
e)，1.60(m,?H
f),?4.20(t,?H
g)，2.01(s,?H
h)，5.58(s,?H
i)，6.15(s,?H
j)?,?1.40(q,?H
k)，0.90(t,?H
l)。
Embodiment 17
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add 3-acryloxy propyl group methyl dimethoxysilane 150g; Catalyst A mberrlite IR-120Na 15g; Stirring also is heated to 60 ℃, drips the water of 22.11g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 50g SWS-F 221 and 300g 3-glycidoxy propyl-triethoxysilicane, when treating that temperature rises to 20 ℃; Drip 29.07g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 10mmHg; Decompression removes low-boiling-point substance under 30 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A17.Record A17 viscosity 50mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.21(s,?H
a),?0.14(s,?H
b),?1.02(t,?H
c),?1.60(m,?H
d)，4.20(t,?H
e)，6.05(m,?H
f),?5.67(b,?H
g)，6.43(b,?H
h)，3.83(q,?H
i)，1.21(t,?H
j),?3.79(t,?H
k)，1.77(m,?H
l)，3.37(t,?H
m)，3.63(m,?H
n)?,?2.86(t,?H
o)，2.63(m,?H
p)。
Embodiment 18
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add 3-acryloxy propyl-triethoxysilicane 100g; Catalyst A mberrlite IR-120Na 15g; Stirring also is heated to 60 ℃, drips the water of 8.41g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 200g dimethyldiethoxysilane and 200g phenyl triethoxysilane, when treating that temperature rises to 70 ℃; Drip 73.46g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 10mmHg; Decompression removes low-boiling-point substance under 70 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A18.Record A18 viscosity 1560mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：7.45(t,?H
a),?7.27(t,?H
b),7.18(t,?H
c),?3.83(q,?H
d)，1.21(t,?H
e)，0.14(s,?H
f),?1.60(m,?H
g)，4.20(t,?H
h)，6.05(m,?H
i)，5.80(b,?H
j),?6.43(b,?H
k)，0.58(t,?H
l)。
Embodiment 19
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add trifluoro propyl Trimethoxy silane 150g; Catalyst A mberrlite IR-120Na 15g; Stirring also is heated to 60 ℃, drips the water of 16.72g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 50g dimethoxydiphenylsilane and 300g methacryloxy methyltrimethoxy silane, when treating that temperature rises to 80 ℃; Drip 29.07g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 10mmHg; Decompression removes low-boiling-point substance under 60 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A19.Record A19 viscosity 1680mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：1.90(m,?H
a),0.58(t,?H
b),3.55(s,?H
c),?7.46(b?H
d)，7.37(t,?H
e)，7.55(t,?H
f),?3.44(s,?H
g)，2.01(s,?H
h)，5.58(s,?H
i)，6.15(s,?H
j)。
Embodiment 20
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add methyltrimethoxy silane 100g; Catalyst A mberrlite IR-120Na 21g; Stirring also is heated to 50 ℃, drips the water of 23.82g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 150g ten difluoro heptyl propyl group methyl dimethoxysilanes and 400g methacryloxy Union carbide A-162, when treating that temperature rises to 70 ℃; Drip 42.31g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 40 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A20.Record A20 viscosity 960mPa.s.Skeleton symbol is following:
1H-NMR(δ/ppm)：0.19(s,?H
a),?3.55(s,?H
b),?0.14(s,?H
c),?1.02(t,?H
d)，1.30(m,?H
e)，1.61(m,?H
f),?5.69(m,?H
g)，3.44(s,?H
h)，2.01(s,?H
i)，5.58(s,?H
j),?6.15(s,?H
k),?3.83(q,?H
l),?1.21(t,?H
m)。
Embodiment 21
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add methacryloxypropyl methyl dimethoxy silane 100g; Catalyst A mberrlite IR-120Na 21g; Stirring also is heated to 50 ℃, drips the water of 26.01g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 150g hexafluoro butyl propyl trimethoxy and 400g dodecyl Trimethoxy silane, when treating that temperature rises to 70 ℃; Drip 45.22g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 40 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A21.Record A21 viscosity 560mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.88(t,?H
a),?1.31(m,?H
b),?1.29(m,?H
c),?1.26(m,?H
d)，1.30(m,?H
e)，0.58(t,?H
f),?3.55(s,?H
g)，3.44(s,?H
h)，2.01(s,?H
i)，5.58(s,?H
j),?6.15(s,?H
k),?1.61(m,?H
l),?1.78(t,?H
m)。
Embodiment 22
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add methacryloxypropyl methyl diethoxy silane 100g; Catalyst A mberrlite IR-120Na 21g; Stirring also is heated to 50 ℃, drips the water of 23.82g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 250g 13 fluoro octyl group trimethoxies and 300g methyltrimethoxy silane, when treating that temperature rises to 70 ℃; Drip 44.13g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 40 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A22.Record A22 viscosity 600mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.19(s,?H
a),?3.55(s,?H
b),?3.44(s,?H
c),?2.01(s,?H
d)，5.58(s,?H
e)，6.15(s,?H
f),?0.14(s,?H
g)，0.58(t,?H
h)，1.60(m,?H
i)。
Embodiment 23
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add methacryloxypropyl methyl diethoxy silane 400g; Catalyst A mberrlite IR-120Na 21g; Stirring also is heated to 50 ℃, drips the water of 25.62g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 50g 17 fluoro decyl trimethoxies and 100g Union carbide A-162, when treating that temperature rises to 70 ℃; Drip 43.56g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 15mmHg; Decompression removes low-boiling-point substance under 50 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A23.Record A23 viscosity 380mPa.s.Skeleton symbol is following
1H-NMR(δ/ppm)：0.19(s,?H
a),?3.83(q,?H
b),?1.21(t,?H
c),?0.14(s,?H
d)，4.20(s,?H
e)，2.01(s,?H
f),5.58(s,?H
g)，6.15(s,?H
h)，3.55(t,?H
i)，0.58(t,?H
j)，1.60(m,?H
k)。
Embodiment 24
In the 1000mL four-hole boiling flask of being furnished with prolong, electronic stirring, Dropping feeder and TM (logical nitrogen protection); Add 3-acryloxy propyl trimethoxy silicane 250g; Catalyst A mberrlite IR-120Na 15g; Stirring also is heated to 60 ℃, drips the water of 12.15g, dropwises back insulation reaction 0.5h;
Afterwards, add the mixture of 120g cyclohexyl trimethoxy silane and 400g 3-glycidoxypropyltrime,hoxysilane, when treating that temperature rises to 70 ℃; Drip 80.33g water again; Dropwise about the insulation reaction 3h of back, cooling is also filtered, again at the highest 10mmHg; Decompression removes low-boiling-point substance under 70 ℃ the condition, can obtain low viscosity functional organic silicon oligopolymer A24.Record A24 viscosity 1720mPa.s.Skeleton symbol is following:
1H-NMR(δ/ppm)：1.49(m,?H
a),?1.53(m,?H
b),?1.60(m,?H
c),?1.40(t,?H
d)，3.55(s,?H
e)，0.58(t,?H
f),?1.50(m,?H
g)，3.37(t,?H
h)，3.63(m,?H
i)，2.86(m,?H
j),?2.63(m,?H
k)，1.60(m,?H
l)，4.20(t,?H
m)，6.05(m,?H
n),?5.80(s,?H
o)，6.43(s,?H
p)。
Preparation two component epoxy organosilicon coating system
Starting material:
Resin Composition:
(1) oligopolymer: A1-A24
(2) epoxide: EHPE-3150CE, S-21, EPOLEAD PB3600, S-28, S-182, S-184, S-60, S-31,1,4-butanediol diglycidyl ether, EPOLEAD GT401
, neopentylglycol diglycidyl ether, D.E.R.736, S-186, D.E.R.732, ERL-4221C
(3) vinylformic acid silicone resin R1-R8 obtains through polymerization, and its composition is as shown in table 1:
Table 1 resin moity
The initiator of note: R1 is an azo-bis-isobutyl cyanide, and the initiator of R2-R6 is a Lucidol, and R7 is an isopropyl benzene hydroperoxide, and R8 is a tert-butyl peroxide; The oligopolymer consumption is the per-cent that accounts for the monomer total amount.The copolyreaction temperature is following: T
R1=70 ℃, T
R2=80 ℃, T
R3=90 ℃, T
R4=100 ℃, T
R5=110 ℃, T
R6=120 ℃, T
R7=130 ℃, T
R8=140 ℃.
Curing agent component
(4) 3-aminopropyl triethoxysilane: DB-550, content is greater than 98.5%,
3-aminopropyl trimethoxysilane: DB-551, content is greater than 98.5%,
(5) secondary amino group oligopolymer CA
1:
(6) secondary amino group oligopolymer CA
2:
(7) secondary amino group oligopolymer CA
3:
(8) secondary amino group oligopolymer CA
4:
(9) secondary amino group oligopolymer CA
5:
Application implementation example 1-24
Application implementation example 1-24 is mixed with varnish with above-mentioned oligopolymer A1-A20, EHPE-3150CE, DB-550 according to the ratio of mass ratio 5:3:2, is applied on the tinplate tin, and in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record the surface drying time 2h-4h of above-mentioned prescription, do solid work time 6h-12h, other performance index are as shown in table 2:
Table 2 results of property
Note: the acid resistance test is in the hydrochloric acid of 15% (wt), to soak 30 days, and alkali resistance is in the NaOH solution of 20% (wt), to soak 7 days; The weathering resistance test duration is 3000h, phenomenon such as film forming matter efflorescence do not occur, comes off, foaming, cracking; The salt fog resistance test duration is 4000h, and every separated 100h observed and recorded once.
Application implementation example 25
A1, A14, S-21, DB-550 are filled a prescription according to the mass ratio preparation of 3:3:2:4, earlier the A1 of 3 mass parts, the A14 of 3 mass parts and the S-21 of 2 mass parts are mixed, add the DB-550 of 4 mass parts again, resin and solidifying agent mass ratio 2:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 4h, do solid work time 6h.
Application implementation example 26
A2, A15, EPOLEAD GT401, DB-550 are filled a prescription according to the mass ratio preparation of 3:3:4:2; Earlier the A2 of 3 mass parts and the A15 of 3 mass parts and the EHPE-3150CE of 4 mass parts are mixed; The DB-551 that adds 2 mass parts again, resin and solidifying agent mass ratio 5:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 3.5h, do solid work time 6h.
Application implementation example 27
A4, A16, S-28, solidifying agent are filled a prescription according to the mass ratio preparation of 10:7:3:5; Earlier the A4 of 10 mass parts and the A16 of 7 mass parts and the EHPE-3150CE of 3 mass parts are mixed; Add the DB-550 of 5 mass parts and the curing agent mixture of CA1 (DB-550 and CA1 mass ratio 2:1) again, resin and solidifying agent mass ratio 4:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 4h, do solid work time 6h.
Application implementation example 28
A6, A17, S-60, solidifying agent are filled a prescription according to the mass ratio preparation of 4:3:2:3; Elder generation is with the A6 of 4 mass parts; The S-186 of the A17 of 3 mass parts and 2 mass parts mixes; Add the DB-550 of 3 mass parts and the mixture of CA2 (DB-550 and CA2 mass ratio 2:1) again, resin and solidifying agent mass ratio 3:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 4h, do solid work time 7h.
Application implementation example 29
With A19, A18, S-182, CA
3According to the mass ratio of 3:3:6:3 preparation prescription, earlier the A19 of 3 mass parts and the A18 of 3 mass parts and the S-21 of 6 mass parts are mixed, add the CA of 3 mass parts again
3, resin and solidifying agent mass ratio 4:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 3h, do solid work time 7h.
Application implementation example 30
With A8, R1, S-184, CA
4According to the mass ratio of 6:1:2:3 preparation prescription, earlier the A8 of 6 mass parts and the R1 of 1 mass parts and the S-21 of 2 mass parts are mixed, add the CA of 3 mass parts again
4, resin and solidifying agent mass ratio 3:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 3h, do solid work time 6h.
Application implementation example 31
With A10, R2, S-31:CA
5According to the mass ratio preparation prescription of 2:1:1:1, with the A10 of 2 mass parts, the S-31 of the R2 of 1 mass parts and 1 mass parts mixes, and adds the CA of 1 mass parts more earlier
5, resin and solidifying agent mass ratio 4:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 5h.
Application implementation example 32
With A14, R3,1; 4-butanediol diglycidyl ether, DB-550 fill a prescription according to the mass ratio preparation of 2:1:1:1; First A14 with 3 mass parts, 1 of the R3 of 1 mass parts and 1 mass parts, the 4-butanediol diglycidyl ether mixes; The DB-550 that adds 1 mass parts again, resin and solidifying agent mass ratio 4:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 6h.
Application implementation example 33
A16, R4, neopentylglycol diglycidyl ether, DB-550 are filled a prescription according to the mass ratio preparation of 1:3:1:1; Elder generation is with the A16 of 1 mass parts; The R4 of 3 mass parts and 1 mass parts neopentylglycol diglycidyl ether mix, and add 1 mass parts DB-550 again, resin and solidifying agent mass ratio 5:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 5h.
Application implementation example 34
A20, R4, D.E.R.736 solidifying agent are filled a prescription according to the mass ratio preparation of 2.5:1:0.5:1; Elder generation is with the A20 of 2.5 mass parts; The R4 of 1 mass parts and 0.5 mass parts D.E.R736 mix; The DB-550 and the CA1 mixed curing agent (DB-550 and CA1 mass ratio 2:1) that add 1 mass parts again, resin and solidifying agent mass ratio 4:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 6h.
Application implementation example 35
A18, R5, S-186, DB-551 are filled a prescription according to the mass ratio preparation of 2:2:1:1, earlier the A18 of 2 mass parts, the R5 and the 1 mass parts S-186 of 2 mass parts are mixed, add the DB-551 of 1 mass parts again, resin and solidifying agent mass ratio 5:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 6h.
Application implementation example 36
A15, R6, D.E.R.732, DB-550 are filled a prescription according to the mass ratio preparation of 2:2:1:1, earlier the A15 of 2 mass parts and the R6 and the 1 mass parts D.E.R732 of 2 mass parts are mixed, add the DB-550 of 1 mass parts again, resin and solidifying agent mass ratio 5:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 6h.
Application implementation example 37
R7, ERL-4221C, DB-550 are filled a prescription according to the mass ratio preparation of 4:1:1, and with the R7 of 4 mass parts, the DB-550 of 1 mass parts and 1 mass parts ERL-4221C mix, resin and solidifying agent mass ratio 5:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 5h.
Application implementation example 38
A14, R8, DB-550 are filled a prescription according to the mass ratio preparation of 2:2:1, earlier the A18 of 2 mass parts and the R8 of 2 mass parts are mixed, add the DB-550 of 1 mass parts again, resin and solidifying agent mass ratio 4:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 5h.
Application implementation example 39
R8, DB-550 are filled a prescription according to the mass ratio preparation of 5:1, and the R8 with 5 mass parts mixes earlier, adds the DB-550 of 1 mass parts again, resin and solidifying agent mass ratio 5:1; Be applied in after mixing on the tinplate, in one week of Air drying, 30 ℃ following dry 21 days.Under 20 ℃ condition, record its surface drying time 2h, do solid work time 5h.
The The performance test results of application implementation example 25-39 is as shown in table 3:
Table 3 The performance test results
Note: the acid resistance test is in the hydrochloric acid of 15% (wt), to soak 30 days, and alkali resistance is in the NaOH solution of 20% (wt), to soak 15 days; The weathering resistance test duration is 3000h, phenomenon such as film forming matter efflorescence do not occur, comes off, foaming, cracking; The salt fog resistance test duration is 4000h, and every separated 100h observed and recorded once.
Can find out that to sum up bi-component epoxy silicone resin of the present invention is used for coating system, and the good impact of performance is arranged.
Above embodiment just lists out the part embodiment in the patent of the present invention, and it is all similar with the embodiment of the invention that other does not enumerate embodiment, and all genus the present invention protect in the extent of competence or with the present invention and protect the relevant content of content, all are protection scope of the present invention.
Claims (10)
1. organosilicon oligopolymer, its general formula is:
(R
1R
2R
3SiO
1/2)
a(R
4R
5SiO)
b(R
6SiO
3/2)
c(SiO
2)
d，
Wherein, R
1, R
2, R
3Be methyl or ethyl; R
4, R
5, R
6Be the alkyl of vinyl or 1-16 carbon atom, or the fluoro-alkyl of the naphthenic base of 1-6 carbon atom, an aryl or 1-18 carbon atom or
,
,
,
A+b+c+d=1, and 0≤a≤0.2,0＜b≤1.0,0＜c≤1.0,0≤d≤0.15.
2. according to the said organosilicon oligopolymer of claim 1, it is characterized in that: the viscosity of said organosilicon oligopolymer is 50-2000mPa.s.
3. method for preparing the described organic low silicon polymers of claim 1, its step comprises:
⑴ be that silane B or a kind of, the mass percent among the C of 0-50% is after 3% cationic exchange resin mixes and is heated to 20-80 ℃ with mass percent; In said mixture, adding mole number is silane alkoxy groups total moles 0.25-1.0 water doubly, insulation reaction 20-40 minute then;
⑵ add a kind of among silane C that mass percent is 50-100% or the B in the mixture of reaction products of step ⑴; Or the mixture of a kind of and silane D among silane C or the B; Reheat is after 20-80 ℃; In said mixture, adding mole number is silane alkoxy groups total moles 0.3-1.0 water doubly, and insulation reaction 2-4 hour then, underpressure distillation obtained said organosilicon oligopolymer behind the cold filtration;
Said silane B, D are the different organoalkoxysilane of structure, and general structure is: R
8Si (R
c)
n(OR
d)
3-n, R wherein
8Fluoro-alkyl for the alkyl of 1-20 carbon atom, naphthenic base, aryl, methoxyl group, oxyethyl group, a 1-18 carbon atom; R
c, R
dBe the alkyl of 1-4 carbon atom, trimethyl silicon based; N is the integer between the 0-3;
The structure of said silane C does
,
,
Or
, R wherein
a, R
bBe the alkyl of 1-4 carbon atom, trimethyl silicon based; R
7Be methyl or H; M is the integer between the 0-3.
4. bicomponent system that comprises the said organosilicon oligopolymer of claim 1 is characterized in that: said bi-component epoxy silicone resin is (2-5) by mass ratio: 1 resin Composition and curing agent component are formed; Said resin portion subpackage contains right and requires organosilicon oligopolymer in 1; Also comprise modified organic silicone resin E and contain among the epoxy resin F of two above epoxy group(ing) one or both, wherein modified organic silicone resin E is obtained by oligopolymer that contains methacryloxy in the organosilicon oligopolymer and acrylic ester monomer copolymerization; Said curing agent component is to contain amino silicoorganic compound M, and the structural formula of M does
, R wherein
9Alkyl for 1-4 carbon atom; R
10Alkyl for H, a 1-4 carbon atom; R
11, R
12Alkyl and alkoxyl group for 1-4 carbon atom; O is the integer between the 1-3, and p is the integer between the 1-20.
5. according to the said bicomponent system of claim 4, it is characterized in that: said modified organic silicone resin E is to be that the organosilicon oligopolymer that contains methacryloxy of 10-90% and acrylic ester monomer that mass percent is 10-90% obtain through copolymerization under 70-140 ℃ by mass percent.
6. according to the said bicomponent system of claim 5, it is characterized in that: the solid content of said modified organic silicone resin E is 60-100%, and viscosity is 100-3000mPa.s.
7. according to the said bicomponent system of claim 4, it is characterized in that: said epoxy resin F is aliphatics or cycloaliphatic epoxy resin, and epoxy equivalent (weight) has at least two epoxide function bases between 100-500.
8. according to the said bicomponent system of claim 4; It is characterized in that: in the said bicomponent system; The mass content of organosilicon component is 50-100%, and said organosilicon component comprises the organosilicon oligopolymer, the organosilicon part in acryl-modified silicone resin resin and the solidifying agent.
9. according to the said bicomponent system of claim 4, it is characterized in that: solid content is 80-100% in the said bicomponent system.
10. the application of the said bicomponent system of claim 4 is characterized in that: said bicomponent system is used for the industrial protection coating system.
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| CN103788865A (en) * | 2012-11-02 | 2014-05-14 | 中冶建筑研究总院有限公司 | Toughening modified polysiloxane paint and use method thereof |
| CN104312362A (en) * | 2014-09-16 | 2015-01-28 | 天长市银狐漆业有限公司 | Antirust paint for improving brightness of finish and preparation method thereof |
| CN107815245A (en) * | 2017-11-02 | 2018-03-20 | 深圳市华宇节耗电子有限公司 | A kind of application of dodecyl triethoxysilane and the tin face protective agent for PCB manufactures and the guard method of tin face |
| WO2019165585A1 (en) * | 2018-02-28 | 2019-09-06 | 邱永兴 | Waterproof adhesive for bonding base layer of photovoltaic panel |
| CN111234136A (en) * | 2020-03-23 | 2020-06-05 | 佛山市天宝利硅工程科技有限公司 | Preparation method of photocuring organic silicon resin system and photocuring film |
| CN111394053A (en) * | 2020-03-03 | 2020-07-10 | 华南理工大学 | Non-flowing underfill with welding assisting function and preparation method thereof |
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| CN103788865A (en) * | 2012-11-02 | 2014-05-14 | 中冶建筑研究总院有限公司 | Toughening modified polysiloxane paint and use method thereof |
| CN103788865B (en) * | 2012-11-02 | 2018-05-11 | 中冶建筑研究总院有限公司 | The polysiloxane coating materials and its application method of a kind of toughening modifying |
| CN104312362A (en) * | 2014-09-16 | 2015-01-28 | 天长市银狐漆业有限公司 | Antirust paint for improving brightness of finish and preparation method thereof |
| CN107815245A (en) * | 2017-11-02 | 2018-03-20 | 深圳市华宇节耗电子有限公司 | A kind of application of dodecyl triethoxysilane and the tin face protective agent for PCB manufactures and the guard method of tin face |
| WO2019165585A1 (en) * | 2018-02-28 | 2019-09-06 | 邱永兴 | Waterproof adhesive for bonding base layer of photovoltaic panel |
| CN111394053A (en) * | 2020-03-03 | 2020-07-10 | 华南理工大学 | Non-flowing underfill with welding assisting function and preparation method thereof |
| CN111394053B (en) * | 2020-03-03 | 2021-10-26 | 华南理工大学 | Non-flowing underfill with welding assisting function and preparation method thereof |
| CN111234136A (en) * | 2020-03-23 | 2020-06-05 | 佛山市天宝利硅工程科技有限公司 | Preparation method of photocuring organic silicon resin system and photocuring film |
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