CN108410417A - A kind of selectivity coheres liquid-state silicon gel and preparation method thereof - Google Patents
A kind of selectivity coheres liquid-state silicon gel and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The present invention relates to silica gel bonding agent fields, cohere liquid-state silicon gel and preparation method thereof more particularly to a kind of selectivity.A kind of selectivity of the present invention coheres liquid-state silicon gel, is prepared by the raw material including following parts by weight:100 parts of cinnamyl group silicone oil, 13 parts of containing hydrogen silicone oil, 05 parts of hydroxy silicon oil, 0.2 2 parts of catalyst, 35 parts of toughener, 80 120 parts of filler, 58 parts of silane coupling agent, 13 parts of weak acid.The invention also discloses the preparation methods that selectivity coheres liquid-state silicon gel.It is high, selective good, stable and environmentally friendly that the selectivity prepared using the present invention coheres liquid-state silicon gel surface autohesion.
Description
Technical field
The present invention relates to silica gel bonding agent fields, cohere liquid-state silicon gel and its preparation side more particularly to a kind of selectivity
Method.
Background technology
The sizing of organic silicon adhesive is made in catalyst by the siloxanes of one or more of line styles, ring-type or branched chain type
Under, the line style of high molecule mass obtained is reacted by balance, addition or condensation etc. or cross-linking type siloxanes forms.Organosilicon
Adhesive mainly has two class of rubber-type and resin type.Organic silicon adhesive has the spies such as high temperature resistant, adhesion strength are stable, persistence is good
Point is widely used in the every field such as aviation, navigation, spaceship, rocket-powered missile, atomic energy, electronic apparatus industry.
However, existing silica gel bonding agent cannot provide good selectivity and adhesive property is bad, limits it and answer
With range, it is therefore desirable to develop a kind of selectivity and cohere liquid-state silicon gel.
Invention content
For this purpose, a kind of selectivity of one aspect of the present invention offer coheres liquid-state silicon gel, by the raw material system for including following parts by weight
It is standby to obtain:
100 parts of cinnamyl group silicone oil, 1-3 parts of containing hydrogen silicone oil, 0-5 parts of hydroxy silicon oil, 0.2-2 parts of catalyst, 3-5 parts of toughener,
80-120 parts of filler, 5-8 parts of silane coupling agent, 1-3 parts of weak acid;
In a kind of technical solution, the ratio of the cinnamyl group silicone oil, containing hydrogen silicone oil and hydroxy silicon oil is 100:1.5:(1-
2.5);In a kind of technical solution, the ratio of the cinnamyl group silicone oil, containing hydrogen silicone oil and hydroxy silicon oil is preferably 100:1.5:
2;
In a kind of technical solution, the catalyst is the mixture of potassium hydroxide and tetramethylammonium hydroxide;
In a kind of technical solution, the toughener is ethylene-vinyl acetate copolymer and acrylonitrile-butadiene-styrene (ABS)
The mixture of copolymer;
In a kind of technical solution, the filler is one or more in white carbon, nano zine oxide and nano yttrium oxide;
In a kind of technical solution, the silane coupling agent is isobutyl triethoxy silane and butadienyl triethoxysilane
Mixture;
In a kind of technical solution, the weak acid is the mixture of citric acid and metasilicic acid;
Another aspect of the present invention is to provide the preparation method that selectivity coheres liquid-state silicon gel, which is characterized in that includes the following steps:
(1)0-5 parts of 100 parts of cinnamyl group silicone oil, 1-3 parts of containing hydrogen silicone oil, hydroxy silicon oil mixing are being stirred according to weight proportion
3-5 parts of toughener of addition under state is mixed, 0.2-2 parts of catalyst is stirring evenly and then adding into, is warming up to 90-110 DEG C, stirs 2-3h,
It is warming up to 130-150 DEG C again, stirs 1-2h, is warming up to 180 degrees Celsius, after stirring 30min, low point is taken off under 0.1MPa vacuum degrees
Sub- 8h, it is spare after cooling;
(2)By 1-3 parts of 80-120 parts of filler, 5-8 parts of silane coupling agent, weak acid progress co-blendeds, then it is ground, institute
It is that 500r/min grinds 30min to state milled processed, and 1000r/min grinds 10min, and 1500r/min grinds 2min, obtains modification
Filler;
(3)By step(1)3/5 and step of product(2)The 2/3 of modified filler is added in stirred tank, is warming up under stiring
120 DEG C, 2h is maintained, remaining modified filler is added, lower maintenance 3h is stirred, remaining 2/5 step is added(1)Product, under stirring
5h, cooled to room temperature is maintained to grind twice on three-roller and cohere liquid-state silicon gel to get to selectivity;
Compared with prior art, beneficial effects of the present invention are:
(1)Three kinds of silicone oil of specific proportioning, the silica gel bonding agent autohesion of preparation is added in prior art basis in the present invention
Height, and to the basis materials such as iron material, PCB, ABS, PET, PBT by good adhesive strength, and it is hardly damaged die surface coating;
(2)The present invention is in advance handled filler in prior art basis, using weak acid, improves filler and basis material
Degrees of fusion;
(3)The present invention uses the filler of special ratios, and silica gel adhesive performance obtained is stable and resistance to ag(e)ing is good;
(4)It is easy to use and environmentally friendly that a kind of selectivity of the present invention coheres liquid-state silicon gel.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with field of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
Hereinafter, the present invention will be described in more detail by embodiment, it should be appreciated that these embodiments are only
Be illustrate and not restrictive.If without specified otherwise, all raw materials are all directly to be purchased from Aladdin reagent.
The properties of material are measured in embodiment using national standard, unless otherwise instructed, the score of component is parts by weight
Number.
Embodiment 1
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 2
(1)100 parts by weight of cinnamyl group silicone oil, 1 parts by weight of containing hydrogen silicone oil, 1 parts by weight of hydroxy silicon oil are mixed, in stirring
Lower 1 parts by weight of addition toughener ethylene-vinyl acetate copolymer and 3 parts by weight of acrylonitrile-butadiene-styrene copolymer,
1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, are warming up to 90-110 DEG C,
3h is stirred, then is warming up to 140 DEG C, stirs 1.5h, is warming up to 180 degrees Celsius, after stirring 30min, is taken off under 0.1MPa vacuum degrees
Low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 3
(1)100 parts by weight of cinnamyl group silicone oil, 2 parts by weight of containing hydrogen silicone oil, 3 parts by weight of hydroxy silicon oil are mixed, in stirring
Lower 1 parts by weight of addition toughener ethylene-vinyl acetate copolymer and 3 parts by weight of acrylonitrile-butadiene-styrene copolymer,
1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, are warming up to 90-110 DEG C,
3h is stirred, then is warming up to 140 DEG C, stirs 1.5h, is warming up to 180 degrees Celsius, after stirring 30min, is taken off under 0.1MPa vacuum degrees
Low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 4
(1)100 parts by weight of cinnamyl group silicone oil, 3 parts by weight of containing hydrogen silicone oil, 5 parts by weight of hydroxy silicon oil are mixed, in stirring
Lower 1 parts by weight of addition toughener ethylene-vinyl acetate copolymer and 3 parts by weight of acrylonitrile-butadiene-styrene copolymer,
1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, are warming up to 90-110 DEG C,
3h is stirred, then is warming up to 140 DEG C, stirs 1.5h, is warming up to 180 degrees Celsius, after stirring 30min, is taken off under 0.1MPa vacuum degrees
Low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 5
(1)100 parts by weight of cinnamyl group silicone oil are mixed with 3 parts by weight of containing hydrogen silicone oil, toughener second is added under stirring
3 parts by weight of 1 parts by weight of alkene-vinyl acetate co-polymer and acrylonitrile-butadiene-styrene copolymer, are stirring evenly and then adding into
1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are warming up to 90-110 DEG C, stir 3h, then be warming up to
140 DEG C, 1.5h is stirred, is warming up to 180 degrees Celsius, after stirring 30min, low molecule 8h is taken off under 0.1MPa vacuum degrees, after cooling
It is spare;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 6
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 0.1 parts by weight of 0.1 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90- is warming up to
110 DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, in 0.1MPa vacuum
De- low molecule 8h under degree, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 7
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.1 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 8
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 0.8 parts by weight of 1.2 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90- is warming up to
110 DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, in 0.1MPa vacuum
De- low molecule 8h under degree, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 9
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
3 parts by weight of toughener ethylene-vinyl acetate copolymer and 2 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 10
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1.5 parts by weight of toughener ethylene-vinyl acetate copolymer and 1.5 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part is measured, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide is stirring evenly and then adding into, is warming up to 90-
110 DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, in 0.1MPa vacuum
De- low molecule 8h under degree, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 11
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
2 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 12
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon and 50 parts by weight of nano zine oxide and silane coupling agent isobutyl triethoxy silane
2 parts by weight and 4 parts by weight of butadienyl triethoxysilane and 1.5 parts by weight of 0.3 parts by weight of weak acid citric acid and metasilicic acid
Co-blended is carried out, is then ground, the milled processed is that 500r/min grinds 30min, 1000r/min grindings
10min, 1500r/min grind 2min, obtain modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 13
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 40 parts by weight of nano zine oxide and 30 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 14
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon and 50 parts by weight of nano yttrium oxide and silane coupling agent isobutyl triethoxy silane
2 parts by weight and 4 parts by weight of butadienyl triethoxysilane and 1.5 parts by weight of 0.3 parts by weight of weak acid citric acid and metasilicic acid
Co-blended is carried out, is then ground, the milled processed is that 500r/min grinds 30min, 1000r/min grindings
10min, 1500r/min grind 2min, obtain modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 15
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 3 parts by weight of agent isobutyl triethoxy silane and 2 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 16
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 5 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 17
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.3 weight of 2 parts by weight of agent isobutyl triethoxy silane and 6 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 18
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.5 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 0.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 19
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.5 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 1.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel.
Embodiment 20
(1)100 parts by weight of cinnamyl group silicone oil, 1.5 parts by weight of containing hydrogen silicone oil, 2 parts by weight of hydroxy silicon oil are mixed, in stirring shape
1 parts by weight of toughener ethylene-vinyl acetate copolymer and 3 weight of acrylonitrile-butadiene-styrene copolymer are added under state
Part, 1 parts by weight of 0.3 parts by weight of catalyst potassium hydroxide and tetramethylammonium hydroxide are stirring evenly and then adding into, 90-110 is warming up to
DEG C, 3h is stirred, then be warming up to 140 DEG C, stir 1.5h, be warming up to 180 degrees Celsius, after stirring 30min, under 0.1MPa vacuum degrees
De- low molecule 8h, it is spare after cooling;
(2)By 50 parts by weight of filler white carbon, 30 parts by weight of nano zine oxide and 20 parts by weight of nano yttrium oxide with it is silane coupled
0.5 weight of 2 parts by weight of agent isobutyl triethoxy silane and 4 parts by weight of butadienyl triethoxysilane and weak acid citric acid
Part and 2.5 parts by weight of metasilicic acid carry out co-blended, are then ground, and the milled processed is that 500r/min is ground
30min, 1000r/min grind 10min, and 1500r/min grinds 2min, obtains modified filler;
(3)By step(1)3/5 parts by weight and step of product(2)2/3 parts by weight of modified filler are added in stirred tank,
It is warming up to 120 DEG C under stirring, maintains 2h, remaining modified filler is added, stirs lower maintenance 3h, remaining 2/5 parts by weight step is added
Suddenly(1)Product, stir and lower 5h, cooled to room temperature maintained grinds twice on three-roller and cohere liquid to get to selective
State silica gel;
Institute's viscosimetric is that selectivity coheres viscosity before liquid-state silicon gel solidification;
Selective test method is that will selectively cohere liquid-state silicon gel and grant sample two sides respectively, on one side Nian Jie with ABS plastic one
Face and die bonding material after curing for 24 hours at room temperature, open mold and sample contacting face, and whether observation die surface coating has
It falls off.
The test data of each embodiment is shown in Table 1.
Table 1
Viscosity/mPas | Surface autohesion/Mpa | Heat-resistant aging/150 DEG C, 168h | Selectivity | |
Embodiment 1 | 5500 | 1.5 | Non- xanthochromia | Nothing falls off |
Embodiment 2 | 5800 | 0.8 | Non- xanthochromia | Nothing falls off |
Embodiment 3 | 5700 | 0.7 | Non- xanthochromia | Nothing falls off |
Embodiment 4 | 5700 | 0.9 | Non- xanthochromia | Nothing falls off |
Embodiment 5 | 5600 | 0.5 | Xanthochromia | It falls off |
Embodiment 6 | 4800 | 0.7 | Non- xanthochromia | Nothing falls off |
Embodiment 7 | 5000 | 1 | Non- xanthochromia | Nothing falls off |
Embodiment 8 | 5200 | 0.9 | Non- xanthochromia | Nothing falls off |
Embodiment 9 | 5200 | 1 | Non- xanthochromia | Nothing falls off |
Embodiment 10 | 5300 | 0.8 | Non- xanthochromia | Nothing falls off |
Embodiment 11 | 5400 | 1.1 | Non- xanthochromia | Nothing falls off |
Embodiment 12 | 5400 | 0.7 | Xanthochromia | It falls off |
Embodiment 13 | 5800 | 1.1 | Non- xanthochromia | Nothing falls off |
Embodiment 14 | 5400 | 0.8 | Xanthochromia | Nothing falls off |
Embodiment 15 | 5200 | 0.8 | Non- xanthochromia | Nothing falls off |
Embodiment 16 | 5400 | 1 | Non- xanthochromia | Nothing falls off |
Embodiment 17 | 5300 | 1.1 | Non- xanthochromia | Nothing falls off |
Embodiment 18 | 5100 | 0.8 | Non- xanthochromia | It falls off |
Embodiment 19 | 5300 | 1.1 | Non- xanthochromia | Nothing falls off |
Embodiment 20 | 5200 | 0.9 | Non- xanthochromia | Nothing falls off |
Liquid-state silicon gel is cohered using the selectivity of MATERIALS METHODS of the present invention, compared in the prior art, surface autohesion is high, selects
Selecting property is good, stable and environmentally friendly.
Example above-mentioned is merely illustrative, some features for explaining the method for the invention.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims
It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (10)
1. a kind of selectivity coheres liquid-state silicon gel, which is characterized in that be prepared by the raw material including following parts by weight:
100 parts of cinnamyl group silicone oil, 1-3 parts of containing hydrogen silicone oil, 0-5 parts of hydroxy silicon oil, 0.2-2 parts of catalyst, 3-5 parts of toughener,
80-120 parts of filler, 5-8 parts of silane coupling agent, 1-3 parts of weak acid.
2. a kind of selectivity as described in claim 1 coheres liquid-state silicon gel, which is characterized in that the cinnamyl group silicone oil contains
The ratio of hydrogen silicone oil and hydroxy silicon oil is 100:1.5:(1-2.5).
3. a kind of selectivity as described in claim 1 coheres liquid-state silicon gel, which is characterized in that the cinnamyl group silicone oil contains
The ratio of hydrogen silicone oil and hydroxy silicon oil is preferably 100:1.5:2.
4. a kind of selectivity as described in claim 1 coheres liquid-state silicon gel, which is characterized in that the catalyst is potassium hydroxide
With the mixture of tetramethylammonium hydroxide.
5. a kind of selectivity as described in claim 1 coheres liquid-state silicon gel, which is characterized in that the toughener is ethylene-vinegar
The mixture of vinyl acetate copolymer and acrylonitrile-butadiene-styrene copolymer.
6. a kind of selectivity as described in claim 1 coheres liquid-state silicon gel, which is characterized in that the filler is white carbon, receives
Rice zinc oxide with it is one or more in nano yttrium oxide.
7. a kind of selectivity as described in claim 1 coheres liquid-state silicon gel, which is characterized in that the silane coupling agent is isobutyl
The mixture of ethyl triethoxy silicane alkane and butadienyl triethoxysilane.
8. a kind of selectivity as described in claim 1 coheres liquid-state silicon gel, which is characterized in that the weak acid is for citric acid and partially
The mixture of silicic acid.
9. selectivity coheres the preparation method of liquid-state silicon gel, which is characterized in that include the following steps:
(1)Weight proportion described in accordance with the claim 1, by 100 parts of cinnamyl group silicone oil, 1-3 parts of containing hydrogen silicone oil, hydroxy silicon oil
0-5 parts of mixing, 3-5 parts of toughener is added under stirring, is stirring evenly and then adding into 0.2-2 parts of catalyst, is warming up to 90-
110 DEG C, 2-3h is stirred, then be warming up to 130-150 DEG C, stir 1-2h, is warming up to 180 degrees Celsius, after stirring 30min,
Low molecule 8h is taken off under 0.1MPa vacuum degrees, it is spare after cooling;
(2)By 1-3 parts of 80-120 parts of filler, 5-8 parts of silane coupling agent, weak acid progress co-blendeds, then it is ground, obtains
To modified filler;
(3)By step(1)3/5 and step of product(2)The 2/3 of modified filler is added in stirred tank, is warming up under stiring
120 DEG C, 2h is maintained, remaining modified filler is added, lower maintenance 3h is stirred, remaining 2/5 step is added(1)Product, under stirring
5h, cooled to room temperature is maintained to grind twice on three-roller and cohere liquid-state silicon gel to get to selectivity.
10. selectivity as claimed in claim 9 coheres the preparation method of liquid-state silicon gel, which is characterized in that step(2)Described in
Milled processed is that 500r/min grinds 30min, and 1000r/min grinds 10min, and 1500r/min grinds 2min.
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CN110128998A (en) * | 2019-05-10 | 2019-08-16 | 矽时代材料科技股份有限公司 | A kind of allyl organic silicon potting adhesive and preparation method thereof |
CN114958188A (en) * | 2022-05-31 | 2022-08-30 | 书香门地集团股份有限公司 | Thermochromic water-based UV coating and preparation method thereof |
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CN106590520A (en) * | 2016-11-14 | 2017-04-26 | 广州市白云化工实业有限公司 | Selective-self-adhesive liquid silicone rubber and preparation method thereof |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110128998A (en) * | 2019-05-10 | 2019-08-16 | 矽时代材料科技股份有限公司 | A kind of allyl organic silicon potting adhesive and preparation method thereof |
CN114958188A (en) * | 2022-05-31 | 2022-08-30 | 书香门地集团股份有限公司 | Thermochromic water-based UV coating and preparation method thereof |
CN114958188B (en) * | 2022-05-31 | 2023-06-06 | 书香门地集团股份有限公司 | Thermochromic water-based UV paint and preparation method thereof |
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