CN110079093B - Wear-resistant organopolysiloxane composition and preparation method thereof - Google Patents
Wear-resistant organopolysiloxane composition and preparation method thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000005299 abrasion Methods 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000005375 organosiloxane group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 3
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 19
- 229920003023 plastic Polymers 0.000 abstract description 13
- 239000004033 plastic Substances 0.000 abstract description 9
- 238000010276 construction Methods 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 33
- 238000001723 curing Methods 0.000 description 17
- 239000004417 polycarbonate Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000009835 boiling Methods 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NJECQESCCSENHG-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octamethyltetrasiletane Chemical compound C[Si]1(C)[Si](C)(C)[Si](C)(C)[Si]1(C)C NJECQESCCSENHG-UHFFFAOYSA-N 0.000 description 3
- 229910020447 SiO2/2 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000003961 organosilicon compounds Chemical group 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- -1 polysiloxane Polymers 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- BPMGYFSWCJZSBA-UHFFFAOYSA-N C[SiH](C)O[SiH3] Chemical compound C[SiH](C)O[SiH3] BPMGYFSWCJZSBA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Abstract
In order to solve the problems of relatively more complicated construction process and higher cost of the existing optical plastic surface hardening process, the invention provides a wear-resistant organopolysiloxane composition, which comprises the following components: component (a 1): methyltrialkoxysilane; component (a 2): a tetraalkoxysilane; component (a 3): a difunctional organoalkoxyalkyl; a component (B): an organopolysiloxane having an epoxy group; a component (C): a catalyst in an amount sufficient to promote polymerization of the composition; a component (D): a curing agent in an amount sufficient to promote curing of the composition. Meanwhile, the invention also discloses a preparation method of the wear-resistant organopolysiloxane composition. The wear-resistant organopolysiloxane composition provided by the invention has good adhesion to optical materials, and effectively improves the wear resistance of the surface of the optical materials.
Description
Technical Field
The invention belongs to the technical field of organic silicon, and particularly relates to a wear-resistant organopolysiloxane composition and a preparation method thereof.
Background
Transparent plastics have been widely used in recent years due to their advantages of good impact resistance, low density, low cost, easy processing and forming, etc. However, the transparent plastic has low surface hardness and poor scratch resistance, and the visibility is impaired and the beauty is affected due to surface scratches caused by friction, dust, wind erosion or surface cleaning and the like in use, so that the service life and the application range of the transparent plastic are affected, and the development of products is severely limited.
One of the existing solutions is to apply an organosilicon abrasion-resistant coating on the surface of a transparent plastic as a protective layer to improve the abrasion resistance, and the technical solutions of organosilicon abrasion-resistant coatings on the surfaces of polycarbonate optical materials disclosed in the chinese patent literature. As described in publication No. CN 101051092, a method for preparing an organosilicon abrasion-resistant coating on the surface of a polycarbonate optical material is disclosed, which comprises the following steps: (1) coating a substrate coating, namely coating the substrate coating on the surface of the polycarbonate optical material in a clean environment, and drying for 2-60 minutes at the temperature of 20-100 ℃; (2) coating the intermediate coating, namely coating the intermediate coating in a clean environment, and drying for 5-120 minutes at 20-100 ℃; (3) and (3) coating the wear-resistant coating, coating the wear-resistant coating in a clean environment, and drying at 20-100 ℃ for 30-300 minutes to obtain the polycarbonate optical material treated by the organic silicon wear-resistant coating. The coating of the invention has excellent performance when forming a coating on the surface of optical plastic, and the surface wear resistance of the optical plastic is greatly improved after the wear-resistant coating is hardened. However, the affinity of the wear-resistant coating to the optical plastic is poor, and when the wear-resistant coating is directly coated on the surface of the optical plastic, the adhesion of the wear-resistant coating on the surface of the optical material is poor, and the wear-resistant coating is easy to fall off after an aging test, so that an intermediate pre-coating layer is needed to improve the adhesion between the wear-resistant coating and the plastic, and the existing organic silicon coating (such as a base coating in patent CN 101051092) with strong affinity to the optical plastic cannot play a role in enhancing the wear resistance due to insufficient hardness and toughness, so that the construction process of the existing optical plastic surface hardening process is relatively complicated, and the cost is high.
Disclosure of Invention
Aiming at the problems of relatively complex construction process and high cost of the existing optical plastic surface hardening process, the invention provides a wear-resistant organopolysiloxane composition and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the present invention provides an abrasion resistant organopolysiloxane composition comprising the following components:
component (a 1): methyltrialkoxysilane;
component (a 2): a tetraalkoxysilane;
component (a 3): a difunctional organoalkoxysilane;
a component (B): an organopolysiloxane having an epoxy group;
a component (C): a catalyst in an amount sufficient to promote polymerization of the composition;
a component (D): a curing agent in an amount sufficient to promote curing of the composition.
Alternatively, component (a 1): component (a 2): component (a 3): the weight ratio of the component (B) is 60-85: 8-30: 4-30: 1 to 3.
Optionally, in the component (a3), the difunctional organoalkoxysilane is selected from one or more of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane and methylphenyldimethoxysilane.
Optionally, in the component (B), the organopolysiloxane with epoxy groups has the following average unit formula:
[MeMeSiO2/2]a1[RMeSiO2/2]b1
wherein Me is methyl and R is
And 0.5<a1<0.85，0.15<b1<0.5。
Optionally, in the component (B), the content of the epoxy group in the organopolysiloxane with epoxy group is 0.20-0.50mol/100 g.
Optionally, the catalyst is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid and acetic acid, and the mass content of the catalyst is 0.01-5% based on 100% of the total mass of the wear-resistant organopolysiloxane composition.
Optionally, the curing agent is an organic amine curing agent, and the mass content of the curing agent is 0.01-1.0% based on 100% of the total mass of the wear-resistant organopolysiloxane composition.
In another aspect, the present invention provides a process for the preparation of an abrasion resistant organopolysiloxane composition comprising the following operative steps:
adding methyl trialkoxysilane, tetraalkoxysilane and difunctional organoalkoxysilane into a reaction container, controlling the temperature of reactants below 40 ℃, dropwise adding a mixture of acid and deionized water, heating to 70-80 ℃ after dropwise adding, keeping the temperature for 3 hours, and heating and distilling to remove a solvent and a low-boiling-point substance in the reactants after keeping the temperature; cooling to room temperature, adding the mixed solvent, the curing agent and the organopolysiloxane with epoxy groups, stirring uniformly, and filtering to obtain the wear-resistant organopolysiloxane composition.
Optionally, the molar ratio of organosiloxane monomer to deionized water is 1: 2.6 to 3.8, said organosiloxane monomer comprising said methyltrialkoxysilane, said tetraalkoxysilane, and said difunctional organoalkoxysilane.
Optionally, the mixed solvent is selected from one or more of methanol, ethanol, isopropanol, n-butanol, benzyl alcohol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, ethyl acetate and butyl acetate.
According to the wear-resistant organopolysiloxane composition provided by the invention, methyl trialkoxysilane, tetraalkoxysilane, difunctional organoalkoxysilane and organopolysiloxane with epoxy groups are combined, so that the obtained organopolysiloxane composition has good adhesion performance to optical materials, can be well formed on the surfaces of the optical materials, and does not need an intermediate precoating layer to realize adhesion of a wear-resistant layer; on the other hand, the organic polysiloxane composition after thermal curing has better wear resistance at normal temperature, effectively improves the wear resistance of the surface of the optical material, and has the advantage of high transparency so as to avoid influencing the optical performance of the optical material.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a wear-resistant organopolysiloxane composition, which comprises the following components:
component (a 1): methyltrialkoxysilane;
component (a 2): a tetraalkoxysilane;
component (a 3): a difunctional organoalkoxysilane;
a component (B): an organopolysiloxane having an epoxy group;
a component (C): a catalyst in an amount sufficient to promote polymerization of the composition;
a component (D): a curing agent in an amount sufficient to promote curing of the composition.
The wear-resistant organopolysiloxane composition is prepared by combining methyl trialkoxysilane, tetraalkoxysilane, difunctional organoalkoxysilane and organopolysiloxane with epoxy groups, so that the obtained organopolysiloxane composition has good adhesion performance to optical materials, can be well formed on the surfaces of the optical materials, and does not need an intermediate precoating layer to realize adhesion of a wear-resistant layer; on the other hand, the organic polysiloxane composition after thermal curing has better wear resistance at normal temperature, effectively improves the wear resistance of the surface of the optical material, and has the advantage of high transparency so as to avoid influencing the optical performance of the optical material.
The wear-resistant organopolysiloxane composition is stable in chemical property, convenient to store and long in storage time.
In some embodiments, component (a 1): component (a 2): component (a 3): the weight ratio of the component (B) is 60-85: 8-30: 4-30: 1 to 3.
The component (a1) and the component (a2) are main resins of the wear-resistant organopolysiloxane composition, and the inventors found that the wear-resistant organopolysiloxane composition prepared from the component (a1) and the component (a2) can exert the wear-resistant property by being mixed with other components, specifically, the content of the component (A3) has a great influence on the wear resistance of the wear-resistant organopolysiloxane composition, and when the content of the component (A3) is too low or too high, the wear resistance is reduced; the content of component (B) has an influence on the adhesion properties of the abrasion-resistant organopolysiloxane composition, and when the content of component (B) is too low, the adhesion-promoting ability is limited, and when the content of component (B) is too high, the abrasion resistance of the abrasion-resistant organopolysiloxane composition is affected.
In some embodiments, in component (a3), the difunctional organoalkoxysilane is selected from one or more of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane.
In some embodiments, in component (B), the epoxy-bearing organopolysiloxane has the following average unit formula:
[MeMeSiO2/2]a1[RMeSiO2/2]b1
wherein Me is methyl and R is
And 0.5<a1<0.85，0.15<b1<0.5。
In some embodiments, the content of epoxy groups in the epoxy group-bearing organopolysiloxane in the component (B) is 0.20 to 0.50mol/100 g.
In some embodiments, the catalyst is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid and acetic acid, and the mass content of the catalyst is 0.01-5% based on 100% of the total mass of the wear-resistant organopolysiloxane composition.
In some embodiments, the curing agent is an organic amine curing agent, and the mass content of the curing agent is 0.01-1.0% based on 100% of the total mass of the wear-resistant organopolysiloxane composition.
Another embodiment of the present invention provides a method for preparing an abrasion resistant organopolysiloxane composition, comprising the following steps:
adding methyl trialkoxysilane, tetraalkoxysilane and difunctional organoalkoxysilane into a reaction container, controlling the temperature of reactants below 40 ℃, dropwise adding a mixture of acid and deionized water, heating to 70-80 ℃ after dropwise adding, keeping the temperature for 3 hours, and heating and distilling to remove a solvent and a low-boiling-point substance in the reactants after keeping the temperature; cooling to room temperature, adding the mixed solvent, the curing agent and the organopolysiloxane with epoxy groups, stirring uniformly, and filtering to obtain the wear-resistant organopolysiloxane composition.
In some embodiments, the dropwise addition of the acid and deionized water is completed within 20min, with stirring occurring simultaneously with the dropwise addition.
In some embodiments, filtration is performed using a filtration device having a pore size of 0.2 microns.
In some embodiments, the abrasion resistant organopolysiloxane composition described above is prepared in a four-neck flask equipped with a condenser, stirrer, and thermometer.
In some embodiments, the molar ratio of organosiloxane monomers to deionized water is 1: 2.6 to 3.8, said organosiloxane monomer comprising said methyltrialkoxysilane, said tetraalkoxysilane, and said difunctional organoalkoxysilane.
In some embodiments, the mixed solvent is selected from one or more of methanol, ethanol, isopropanol, n-butanol, benzyl alcohol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, ethyl acetate, and butyl acetate.
The present invention will be further illustrated by the following examples.
Synthesis example 1
978g of methyltrimethoxysilane, 233g of tetraethoxysilane and 150g of dimethyldimethoxysilane are mixed; putting into a reaction bottle, cooling to 20 ℃, and dripping 390.0g of dilute hydrochloric acid solution with pH value of 5 in 20 minutes; after dripping, heating to 70 ℃, stirring for 3 hours, carrying out reduced pressure distillation and concentration by using a vacuum water pump, removing the solvent and low boiling point substances under reduced pressure, cooling when the solid content is 35 +/-2%, and adding the mixed solvent and the curing agent while cooling; the silicone composition was obtained as E1.
In the synthesis process of the component, the addition amount of the dimethyl dimethoxy silane is 11 percent, and the mol ratio of the organosiloxane monomer to the mol of the deionized water is 1: 2.5.
synthesis example 2
966g of methyltrimethoxysilane, 233g of tetraethoxysilane and 51g of dimethyldimethoxysilane; putting into a reaction bottle, cooling to 20 ℃, dropwise adding 390.0g of dilute hydrochloric acid solution with pH value of 5 within 20 minutes, heating to 70 ℃ after dropwise adding, stirring for 3 hours, carrying out reduced pressure distillation and concentration by using a vacuum pump, removing the solvent and low boiling point substances under reduced pressure, cooling when the solid content is 35 +/-2%, and adding the mixed solvent and the curing agent while cooling; the silicone composition was obtained as E2.
In the synthesis process of the component, the addition amount of dimethyl dimethoxy silane is 4%, and the mol ratio of the organic siloxane monomer to the deionized water is 1: 2.5.
synthesis example 3
1045g of methyltrimethoxysilane, 230g of tetraethoxysilane and 53g of dimethyldimethoxysilane; putting into a reaction bottle, cooling to 20 ℃, dropwise adding 380.0g of dilute hydrochloric acid solution with pH of 5 within 20 minutes, heating to 70 ℃ after dropwise adding, stirring for 3 hours, carrying out reduced pressure distillation and concentration by using a vacuum pump, removing the solvent and low boiling point substances under reduced pressure, cooling when the solid content is 35 +/-2%, and adding the mixed solvent and the curing agent while cooling; the silicone composition was obtained as E3.
In the synthesis process of the component, the addition amount of dimethyl dimethoxy silane is 4%, and the mol ratio of the organic siloxane monomer to the deionized water is 1: 2.3.
synthesis example 4
1045g of methyltrimethoxysilane, 217g of tetraethoxysilane and 80g of dimethyldisiloxane; putting into a reaction bottle, cooling to 20 ℃, dropwise adding 460.0g of dilute hydrochloric acid solution with pH of 5 within 20 minutes, heating to 70 ℃ after dropwise adding, stirring for 3 hours, carrying out reduced pressure distillation and concentration by using a vacuum pump, removing the solvent and low boiling point substances under reduced pressure, cooling when the solid content is 35 +/-2%, and adding the mixed solvent and the curing agent while cooling; the silicone composition was obtained as E4.
The addition amount of the dimethyl dimethoxy silane in the synthesis process of the component is 6 percent, and the mol ratio of the organosiloxane monomer to the mol of the deionized water is 1: 3.0.
synthesis example 5
Adding 230g of octamethylcyclotetrasilane, (3-glycidoxypropyl) methyldimethoxysilane 193g and ethyl acetate 50g into a flask, stirring uniformly, dropwise adding an octanol solution of chloroplatinic acid (the concentration of platinum is 5 wt%), heating to 80 ℃, reacting for 10 hours, vacuumizing to-0.095 MPa, heating to 170 ℃, and vacuumizing to remove low-boiling-point substances to obtain a resin F1 with the following structure:
[Me2SiO2/2]0.78[RMeSiO2/2]0.22
wherein R is
This component is an organosilicon compound having a viscosity of 50 mPas at 25 ℃. The content of epoxy groups was 0.23mol/100 g.
Synthesis example 6
Adding 220g of octamethylcyclotetrasilane, (3-glycidoxypropyl) methyldimethoxysilane 115g and ethyl acetate 50g into a flask, stirring uniformly, dropwise adding an octanol solution of chloroplatinic acid (the concentration of platinum is 5 wt%), heating to 80 ℃, reacting for 10 hours, vacuumizing to-0.095 MPa, heating to 170 ℃, and vacuumizing to remove low-boiling-point substances to obtain a resin F2 with the following structure:
[Me2SiO2/2]0.85[RMeSiO2/2]0.15
wherein R is
This component is an organosilicon compound having a viscosity of 43 mPas at 25 ℃. The content of epoxy groups was 0.17mol/100 g.
Synthesis example 7
Adding 67g of octamethylcyclotetrasilane, (3-glycidoxypropyl) methyldimethoxysilane 242g and ethyl acetate 50g into a flask, stirring uniformly, dropwise adding an octanol solution of chloroplatinic acid (the concentration of platinum is 5 wt%), heating to 80 ℃, reacting for 10 hours, vacuumizing to-0.095 MPa, heating to 170 ℃, and vacuumizing to remove low-boiling-point substances to obtain a resin F3 with the following structure:
[Me2SiO2/2]0.45[RMeSiO2/2]0.55
wherein R is
This component is an organosilicon compound having a viscosity of 68 mPas at 25 ℃. The content of epoxy groups was 0.49mol/100 g.
Performance testing
The compositions shown in Table 1 were mixed (parts by weight of each composition) to give examples and comparative examples of the compositions provided by the present invention.
The examples prepared above and comparative examples were subjected to the following performance tests:
[ ADHESIVE ] OF
Dip-coating the obtained composition on a PC substrate, curing at 120 ℃ for 2h to form a coating with the thickness of 3-5 microns on the surface of the PC substrate, scribing hundreds of grids by using a scriber, and testing the adhesive force by using a 3M adhesive tape;
[ boiling adhesion ]
The obtained composition is dip-coated on a PC substrate and cured at 120 ℃ for 2h, so that a coating with the thickness of 3-5 microns is formed on the surface of the PC substrate. Putting the cured base material into 100 ℃ boiling water, boiling the base material in water for 1h, taking out the base material, wiping the base material clean, scratching hundreds of grids by using a grid scratching device, and testing the boiling adhesion by using a 3M adhesive tape;
[ WEAR-RESISTANT ] FOR PREVENTING RAIN
The obtained composition is dip-coated on a PC substrate and cured at 120 ℃ for 2h, so that a coating with the thickness of 3-5 microns is formed on the surface of the PC substrate. Then, using No. 4 steel wool to rub back and forth for 20 times under the gravity of a 500g weight, and observing the scratching condition of the coating;
[ surface tackiness ]
The obtained composition is dip-coated on a PC substrate and cured at 120 ℃ for 2h, so that a coating with the thickness of 3-5 microns is formed on the surface of the PC substrate. The coating was cooled to 25 ℃ and tested for surface tack by hand.
The test results obtained are filled in Table 1.
TABLE 1
Remarking: among them, o indicates excellent performance, o indicates good performance, and Δ indicates poor performance.
As can be seen from the test results in Table 1, the composition provided by the technical scheme of the embodiment of the invention has better adhesion performance to a PC substrate, the adhesion between the wear-resistant coating and the PC substrate is realized without an intermediate pre-coating layer, and the formed PC substrate surface coating has better wear resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. An abrasion resistant organopolysiloxane composition, characterized by comprising the following components:
component (a 1): methyltrialkoxysilane;
component (a 2): a tetraalkoxysilane;
component (a 3): a difunctional organoalkoxysilane;
a component (B): an organopolysiloxane having an epoxy group;
a component (C): a catalyst in an amount sufficient to promote polymerization of the composition;
a component (D): a curing agent in an amount sufficient to promote curing of the composition;
component (a 1): component (a 2): component (a 3): the weight ratio of the component (B) is 60-85: 8-30: 4-30: 1 to 3.
2. The abrasion resistant organopolysiloxane composition according to claim 1, wherein in component (a3), the difunctional organoalkoxysilane is selected from one or more of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane.
3. The abrasion-resistant organopolysiloxane composition according to claim 1, wherein in component (B), the epoxy-bearing organopolysiloxane has the following average unit formula:
[MeMeSiO2/2]a1[RMeSiO2/2]b1
wherein Me is methyl and R is
And 0.5<a1<0.85，0.15<b1<0.5。
4. The abrasion-resistant organopolysiloxane composition according to claim 1, wherein in component (B), the content of epoxy groups in the epoxy group-bearing organopolysiloxane is 0.20 to 0.50mol/100 g.
5. The abrasion resistant organopolysiloxane composition according to claim 1, wherein the catalyst is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, and the mass content of the catalyst is 0.01% to 5% based on 100% of the total mass of the abrasion resistant organopolysiloxane composition.
6. The wear-resistant organopolysiloxane composition according to claim 1, wherein the curing agent is an organic amine curing agent, and the mass content of the curing agent is 0.01% to 1.0% based on 100% of the total mass of the wear-resistant organopolysiloxane composition.
7. A process for the preparation of an abrasion-resistant organopolysiloxane composition, characterized by the following operating steps:
adding methyl trialkoxysilane, tetraalkoxysilane and difunctional organoalkoxysilane into a reaction container, controlling the temperature of reactants below 40 ℃, dropwise adding a mixture of acid and deionized water, heating to 70-80 ℃ after dropwise adding, keeping the temperature for 3 hours, and heating and distilling to remove a solvent and a low-boiling-point substance in the reactants after keeping the temperature; cooling to room temperature, adding the mixed solvent, the curing agent and the organopolysiloxane with epoxy groups, stirring uniformly, and filtering to obtain the wear-resistant organopolysiloxane composition;
methyltrialkoxysilane: tetraalkoxysilane: difunctional organoalkoxysilane: the weight ratio of the organopolysiloxane with epoxy groups is 60-85: 8-30: 4-30: 1 to 3.
8. The method of preparing an abrasion resistant organopolysiloxane composition according to claim 7, wherein the molar ratio of organosiloxane monomer to deionized water is 1: 2.6 to 3.8, said organosiloxane monomer comprising said methyltrialkoxysilane, said tetraalkoxysilane, and said difunctional organoalkoxysilane.
9. The method for preparing an abrasion resistant organopolysiloxane composition according to claim 7, wherein the mixed solvent is selected from one or more of methanol, ethanol, isopropanol, n-butanol, benzyl alcohol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, ethyl acetate, and butyl acetate.
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