CN102206478A - Environment-friendly silyl-terminated polyether sealant and preparation method thereof - Google Patents
Environment-friendly silyl-terminated polyether sealant and preparation method thereof Download PDFInfo
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- CN102206478A CN102206478A CN201110102288XA CN201110102288A CN102206478A CN 102206478 A CN102206478 A CN 102206478A CN 201110102288X A CN201110102288X A CN 201110102288XA CN 201110102288 A CN201110102288 A CN 201110102288A CN 102206478 A CN102206478 A CN 102206478A
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Abstract
This invention relates to an environment-friendly silyl-terminated polyether sealant and a preparation method thereof. The sealant includes the following components of: 50 parts of silyl-terminated polyether, 3-30 parts of reactive diluent, 10-70 parts of filler, 5-30 parts of reinforcing agent, 0.1-5 parts of moisture scavenger, 0.1-5 parts of adhesive promoter and 0.1-2 parts of curing promoter. The preparation method includes the following steps of: adding the silyl-terminated polyether, the reactive diluent, the filler and the reinforcing agent into a stirring tank in sequence, and stirring for 1-4 hours under the condition of 60-100 DEG C and dry inert gas; cooling to below 40 DEG C, then adding the moisture scavenger, the adhesive promoter and the curing promoter, stirring for 15-30 min under vacuum. In the components of the prepared silyl-terminated polyether sealant disclosed by the invention, the reactive diluent is added, and additional solvent and plasticizer do not need to be added to the components, therefore, the prepared silyl-terminated polyether sealant has no discharge pollution of organic micromolecules, such as the solvent, the plasticizer and so on. In addition, the environment-friendly silyl-terminated polyether sealant discloses by the invention has moderate product viscosity and is convenient for extruding operation during construction.
Description
Technical field
The present invention relates to the polyether seal glue technical field, particularly relate to a kind of environment-friendly type silyl-terminated polyether seal gum and preparation method thereof.
Background technology
In the prior art, except that pitch, tar etc. some are inexpensive, the seal gum of lower performance, present seal gum market also includes poly-sulphur class seal gum, silicone seal gum and polyurethanes seal gum, and these poly-sulphur class seal gums, silicone seal gum and polyurethanes seal gum have occupied domestic most market.
Wherein, poly-sulphur class seal gum once obtained to use widely, but because of shortcomings such as its frowziness, slow, the easy age hardening of low-temperature curing speed, poor durability, developed further and limited it.The silicone seal gum has advantages such as the low temperature kindliness is good, excellent electric insulation, chemical stability, hydrophobic moistureproofness, but its intensity is low, sticking power and antifouling property are poor, and cost is also higher relatively.Polyurethanes seal gum adhesiveproperties is strong, mechanics mechanical property excellence, acid and alkali-resistance, organic solvent-resistant, but its easy variable color when using, and comparatively responsive in storing to moisture, environment friendly also needs further to improve.
Along with the continuous development of society, the requirement of seal gum product quality is promoted day by day, relevant laws and regulations are day by day strict, and the performance of above-mentioned several seal gums can not satisfy the new demand in market.Therefore, the novel seal glue of Development and Production high-performance, more environmental protection becomes the general trend of seal gum industry.
The silyl-terminated polyether seal gum is the important development direction of seal gum industry, its structure is special, have many advantages of silicone seal gum and polyurethanes seal gum concurrently, have higher tear strength and breaking tenacity, and moderate modulus, elongation at break and hardness, and environmentally safe is a kind of seal gum of excellence.At present, the silyl-terminated polyether seal gum is the production and the use of existing certain scale in the international market, and in the 70's of 20th century, silicon-modified polyether seal gum technology is succeeded in developing in Japan, and comes into the market in the 80's.Europe and the silane-modified seal gum of the U.S. be development in succession also, all there are silicon modification seal gum product in Henkel, Degussa and the companies such as U.S. Witco, Crompton of Germany, wherein, the Degussa company of Germany has developed the silicon-modified polyether seal gum, by in the silicon-modified polyether seal gum, adding various suitable adhesion promoters, improve the adhesiveproperties and the mechanical property of seal gum effectively, had more perfect product technology.Relevant patent report is also more, as: JP 11124509 (1999) reports work out 6 hours curable silyl-terminated polyether seal gums of room temperature.WO 9919405 (1999) report developments obtain the silyl-terminated polyether seal gum that elongation is 830 ﹪.JP 05287186 (1993) report configures can be by quickening the silyl-terminated polyether seal gum of weather resistant experiment in 1800 hours.JP 1143599 (1999) reports make and can expose 3 months free of contamination silyl-terminated polyether seal gums etc. out of doors, and domestic relevant matured product is then more rare.
In the prior art; in order to guarantee the performance of silyl-terminated polyether seal gum; usually can select for use molecular weight higher; the bigger silyl-terminated polyether of viscosity is as base polymer; this will cause the viscosity height of seal gum product; need solubilizing agent or softening agent viscosity reduction, otherwise viscosity is excessive, be difficult to satisfy in the seal gum construction process about extrudability requirement.Yet the use of solvent or softening agent can bring certain environmental pollution again.Above problem has limited the application of silyl-terminated polyether seal gum to a certain extent.
Therefore, bigger at end-silicane-group polyether viscosity in the prior art, the environmental pollution problems that needs use solvent or softening agent viscosity reduction in the layoutprocedure and cause, need badly: a kind of solvent-free and softening agent is provided, product viscosity is moderate, and easy to operate environment-friendly type silyl-terminated polyether seal gum and preparation method thereof is extruded in construction.
Summary of the invention
One of purpose of the present invention is to avoid weak point of the prior art and a kind of solvent-free and softening agent is provided, and product viscosity is moderate, and easy to operate environment-friendly type silyl-terminated polyether seal gum is extruded in construction.
Two of purpose of the present invention is to avoid weak point of the prior art and provides a kind of technology simple, easy to operate, the preparation method of practical environment-friendly type silyl-terminated polyether seal gum, adopt solvent-free and softening agent in the environment-friendly type silyl-terminated polyether seal gum of this preparation method preparation, can avoid the exhaust emission of organic molecule, and product viscosity is moderate, and construction is extruded easy to operate.
Purpose of the present invention is achieved through the following technical solutions:
On the one hand, the invention provides a kind of environment-friendly type silyl-terminated polyether seal gum, comprise the raw material of following weight part:
50 parts of silyl-terminated polyethers
3～30 parts of reactive thinners
10～70 parts of fillers
5～30 parts of strengthening agents
0.1～5 part of moisture content scavenging agent
0.1～5 part of adhesive accelerant
0.1～2 part of curing catalyst.
A kind of environment-friendly type silyl-terminated polyether seal gum comprises the raw material of following weight part:
50 parts of silyl-terminated polyethers
3～15 parts of reactive thinners
10～40 parts of fillers
5～20 parts of strengthening agents
0.1～2.5 part of moisture content scavenging agent
0.1～5 part of adhesive accelerant
0.1～2 part of curing catalyst.
A kind of environment-friendly type silyl-terminated polyether seal gum comprises the raw material of following weight part:
50 parts of silyl-terminated polyethers
15～30 parts of reactive thinners
40～70 parts of fillers
20～30 parts of strengthening agents
2.5～5 parts of moisture content scavenging agents
0.1～5 part of adhesive accelerant
0.1～2 part of curing catalyst.
Above-mentioned silyl-terminated polyether comprises any in the polyoxytrimethylene ether of the polyoxytrimethylene ether of polyoxytrimethylene ether, terminal methyl diethoxy silyl polyoxytrimethylene ether, end triethoxysilyl of the polyoxytrimethylene ether of holding trimethoxysilyl, terminal methyl dimethoxy silyl and terminal methyl trimethoxysilyl.
Above-mentioned reactive thinner be molecular weight less than 1500, end group is the polyoxytrimethylene ether of hydrolyzable silane base.
Above-mentioned hydrolyzable silane base is any in dimethylmethoxysilylgroups groups and the dimethyl (ethoxymethyl) silylation.
Above-mentioned filler be Paris white, talcum powder, through the Paris white of surface modification and in the wollastonite powder any or several; Described strengthening agent is carbon black or white carbon black; Described moisture content scavenging agent is the silane coupling agent or the oxazole alkanes moisture content scavenging agent of the reaction that easily is hydrolyzed.
Above-mentioned adhesive accelerant be in gamma-mercaptopropyltriethoxysilane, γ-An Bingjisanjiayangjiguiwan, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-methacryloxypropyl trimethoxy silane and γ-glycidyl ether oxygen base propyl trimethoxy silicane any or several.
Above-mentioned curing catalyst be in compound accelerant, dibutyl tin laurate and the modification organotin catalysts of organo-tin compound and alkylamine any or several.
On the other hand, the present invention also provides a kind of preparation method of environment-friendly type silyl-terminated polyether seal gum, comprising:
Press formula ratio successively will, silyl-terminated polyether, reactive thinner, filler and strengthening agent join in the stirring tank, under 60～100 ℃, the condition of exsiccant protection of inert gas, mix and stir 1～4h; Be cooled to below 40 ℃, add moisture content scavenging agent, adhesive accelerant, curing catalyst again, under vacuum condition, stir 15～30min, obtain environment-friendly type silyl-terminated polyether seal gum.
Beneficial effect of the present invention: a kind of environment-friendly type silyl-terminated polyether seal gum of the present invention comprises 0.1～2 part of 50 parts of silyl-terminated polyethers, 3～30 parts of reactive thinners, 10～70 parts of fillers, 5～30 parts of strengthening agents, 0.1～5 part of moisture content scavenging agent, 0.1～5 part of adhesive accelerant and curing catalyst.The preparation method of a kind of environment-friendly type silyl-terminated polyether seal gum of the present invention, comprise by formula ratio and successively will, silyl-terminated polyether, reactive thinner, filler and strengthening agent join in the stirring tank successively, under 60～100 ℃, the condition of exsiccant protection of inert gas, mix and stir 1～4h; Be cooled to below 40 ℃, add moisture content scavenging agent, adhesive accelerant, curing catalyst again, under vacuum condition, stir 15～30min, obtain environment-friendly type silyl-terminated polyether seal gum.
It is bigger to the present invention is directed to silyl-terminated polyether viscosity, need to use solvent or softening agent viscosity reduction in the layoutprocedure, thereby cause environmental pollution problems, by in raw material, adding reactive thinner, solvent and softening agent have been avoided in component, adding in addition, make organic molecule exhaust emissions such as solvent-free in the silyl-terminated polyether seal gum of preparation, softening agent, make that the product viscosity of preparation is moderate, construction is extruded easy to operate, can be applied to the sealing and the bonding of various material, applied range has bigger market outlook.
Reactive thinner claims reactive solvents again.Can dissolve base polymer or disperse filler as usual vehicle, can in the material cured process, participate in curing reaction again, form non-volatile, do not move component and stay a compounds in the material.The principal character of reactive thinner is that oneself viscosity is low, can use as solvent, and contain active group in the molecule, can participate in curing reaction, and the performance of cured glue layer is not generally had influence, can also play toughening effect sometimes.Just can be used as the reactive thinner of Resins, epoxy as polypropylene glycol diglycidyl ether, in the time of 25 ℃, its viscosity is below 500 m PaS, and is low even have only about 40m PaS, can effectively reduce the viscosity of Resins, epoxy; And institute's band oxygen groups can participate in the curing cross-linking reaction of Resins, epoxy in its molecule, does not have volatilization, overflows, and can not cause organic exhaust emission.
Further, reactive thinner of the present invention adopts molecular weight less than 1500, end group is that the polyoxytrimethylene ether of dimethylmethoxysilylgroups groups or dimethyl (ethoxymethyl) silylation is as reactive thinner, the reactive thinner that the present invention adopts with active group be hydrolyzable silylation, wherein, the molecular formula of reactive thinner is as follows:
Perhaps
Wherein
For
Or
,
Be alkyl, n is 1～20.
Because the present invention adopts band active group, molecular weight to be lower than 1500 end-silicane-group polyoxytrimethylene ether as reactive thinner, because this reactive thinner viscosity is low, can dissolve or disperse other component of seal gum, reduced system viscosity effectively, do not need to add in addition solvent and softening agent viscosity reduction when joining glue, just each component of silyl-terminated polyether seal gum can be mixed.
The specific embodiment mode
With the following Examples the present invention is further described:
Need to prove that the compound viscosity testing conditions to seal gum in following examples is: use Advanced rheometer AR2000 type rheometer, 20mm vertebral plate, 25 ℃ of temperature.
Embodiment 1
A kind of environment-friendly type silyl-terminated polyether seal gum comprises the raw material of following weight part:
50 parts in terminal methyl dimethoxy silyl polyoxytrimethylene ether
15 parts of end dimethylmethoxysilylgroups groups
70 parts of Paris whites
5 parts of carbon blacks
5 parts of vinyltrimethoxy silanes
5 parts of gamma-mercaptopropyltriethoxysilanes
2 parts of dibutyl tin laurates.
Concrete, the molecular weight of end dimethylmethoxysilylgroups groups is lower than 1500.
The preparation method of the environment-friendly type silyl-terminated polyether seal gum of present embodiment, comprise: join in the stirring tank successively 50 parts in terminal methyl dimethoxy silyl polyoxytrimethylene ether, 15 parts of dimethylmethoxysilylgroups groups of end, 70 parts of Paris whites, carbon black for 5 parts, under 100 ℃, the condition of exsiccant nitrogen protection, mix and stir 4h; Be cooled to below 40 ℃; add 5 parts of vinyltrimethoxy silanes, 5 parts of gamma-mercaptopropyltriethoxysilanes, 2 parts of dibutyl tin laurates again; under the drying nitrogen protection; stir 30min; obtain the environment-friendly type silyl-terminated polyether seal gum of embodiment 1; according to testing conditions, recording its compound viscosity is 1780PaS.
Embodiment 2
A kind of environment-friendly type silyl-terminated polyether seal gum comprises the raw material of following weight part:
50 parts in end trimethoxysilyl polyoxytrimethylene ether
3 parts of end dimethyl (ethoxymethyl) silylation
Through 50 parts of the Paris whites of surface modification
10 parts of carbon blacks
1 part of vinyltrimethoxy silane
1 part of γ-An Bingjisanjiayangjiguiwan
0.5 part of modification organotin catalysts.
Concrete, the molecular weight of end dimethyl (ethoxymethyl) silylation is lower than 1500.
The preparation method of the environment-friendly type silyl-terminated polyether seal gum of present embodiment, comprise: will hold 50 parts in trimethoxysilyl polyoxytrimethylene ether, 3 parts of reactive thinners, join in the stirring tank successively for 10 parts through 50 parts of Paris whites, the carbon black of surface modification, under 60 ℃, the condition of exsiccant nitrogen protection, mix and stir 1h; Be cooled to below 40 ℃; add 1 part of vinyltrimethoxy silane, 1 part of γ-An Bingjisanjiayangjiguiwan, 0.5 part of modification organotin catalysts again; under the drying nitrogen protection; stir 15min; obtain the environment-friendly type silyl-terminated polyether seal gum of embodiment 2; according to testing conditions, recording its compound viscosity is 3550PaS.
Embodiment 3
A kind of environment-friendly type silyl-terminated polyether seal gum comprises the raw material of following weight part:
50 parts in terminal methyl diethoxy silyl polyoxytrimethylene ether
15 parts of end dimethylmethoxysilylgroups groups
Through 40 parts of the Paris whites of surface modification
10 parts of white carbon blacks
2 parts of vinyltrimethoxy silanes
2 parts of N-β-aminoethyls-γ-An Bingjisanjiayangjiguiwan
1 part of dibutyl tin laurate.
Concrete, the molecular weight of end dimethylmethoxysilylgroups groups is lower than 1500.
The preparation method of the environment-friendly type silyl-terminated polyether seal gum of present embodiment, comprise: with 50 parts in terminal methyl diethoxy silyl polyoxytrimethylene ether, 15 parts of reactive thinners, join in the stirring tank successively for 10 parts through 40 parts of Paris whites, the white carbon black of surface modification, under 80 ℃, the condition of exsiccant nitrogen protection, mix and stir 3h; Be cooled to below 40 ℃; add 2 parts of vinyltrimethoxy silanes, N-β-aminoethyl-2 parts of γ-An Bingjisanjiayangjiguiwans, 1 part of dibutyl tin laurate again; under the drying nitrogen protection; stir 30min; obtain the environment-friendly type silyl-terminated polyether seal gum of embodiment 3; according to testing conditions, record its compound viscosity 1530PaS.
Embodiment 4
A kind of environment-friendly type silyl-terminated polyether seal gum comprises the raw material of following weight part:
50 parts in end triethoxysilyl polyoxytrimethylene ether
20 parts of end dimethyl (ethoxymethyl) silylation
50 parts of the Paris whites of surface modification
20 parts of carbon blacks
1.5 parts of vinyltrimethoxy silanes
1.5 parts of γ-methacryloxypropyl trimethoxy silane
1 part of dibutyl tin laurate.
Concrete, the molecular weight of end dimethyl (ethoxymethyl) silylation is lower than 1500.
The preparation method of the environment-friendly type silyl-terminated polyether seal gum of present embodiment, comprise: will hold 50 parts in triethoxysilyl polyoxytrimethylene ether, 20 parts of reactive thinners, 50 parts of the Paris whites of surface modification, carbon black to join in the stirring tank successively for 20 parts, under 80 ℃, the condition of exsiccant nitrogen protection, mix and stir 2h; Be cooled to below 40 ℃; add 1.5 parts of vinyltrimethoxy silanes, 1.5 parts of γ-methacryloxypropyl trimethoxy silane, 1 part of dibutyl tin laurate again; under the drying nitrogen protection; stir 30min; obtain the environment-friendly type silyl-terminated polyether seal gum of embodiment 4; according to testing conditions, record its compound viscosity 1310PaS.
Embodiment 5
A kind of environment-friendly type silyl-terminated polyether seal gum comprises the raw material of following weight part:
50 parts in end trimethoxysilyl polyoxytrimethylene ether
20 parts of end dimethyl (ethoxymethyl) silylation
Through 50 parts of the Paris whites of surface modification
20 parts of white carbon blacks
1.5 parts of vinyltrimethoxy silanes
1.5 parts of γ-glycidyl ether oxygen base propyl trimethoxy silicane
1 part of dibutyl tin laurate.
Concrete, the molecular weight of end dimethyl (ethoxymethyl) silylation is lower than 1500.
The preparation method of the environment-friendly type silyl-terminated polyether seal gum of present embodiment comprises: will hold 50 parts in trimethoxysilyl polyoxytrimethylene ether, 30 parts of reactive thinners, join in the stirring tank successively for 20 parts through 50 parts of Paris whites, the white carbon black of surface modification; Under 80 ℃, the condition of exsiccant nitrogen protection, mix and stir 2h; Be cooled to below 40 ℃; add 1.5 parts of vinyltrimethoxy silanes, γ-1.5 parts of glycidyl ether oxygen base propyl trimethoxy silicanes, 1 part of dibutyl tin laurate again; under the drying nitrogen protection; stir 30min; obtain implementing 5 environment-friendly type silyl-terminated polyether seal gum; according to testing conditions, record its compound viscosity 1030PaS.
Comparative Examples
In stirring tank, add 50 parts in terminal methyl dimethoxy silyl polyoxytrimethylene ether, 70 parts of Paris whites, 5 parts of carbon blacks (with reactive thinner) successively, under 100 ℃, the condition of exsiccant nitrogen protection, mix and stir 4h; Be cooled to below 40 ℃; add 5 parts of vinyltrimethoxy silanes, 5 parts of gamma-mercaptopropyltriethoxysilanes, 2 parts of dibutyl tin laurates; under the drying nitrogen protection; stir 3min; obtain the environment-friendly type silyl-terminated polyether seal gum of Comparative Examples; according to testing conditions, recording its compound viscosity is 4380PaS.
The contrast table such as the following table 1 of the compound viscosity of environment-friendly type silyl-terminated polyether seal gum among the embodiment 1 to embodiment 5 and the environment-friendly type silyl-terminated polyether seal gum in the Comparative Examples:
The contrast table of table 1 compound viscosity
| ? | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Compound viscosity PaS | 4380 | 1780 | 3550 | 1530 | 1310 | 1030 |
This shows that add among the embodiment of reactive thinner, because reactive thinner viscosity is low, other component that can dissolve or disperse seal gum has reduced system viscosity effectively, makes that prepared product viscosity is moderate, construction is extruded easy to operate.
Should be noted that at last; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although the present invention has been done to explain with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the essence and the scope of technical solution of the present invention.
Claims (10)
1. an environment-friendly type silyl-terminated polyether seal gum is characterized in that, comprises the raw material of following weight part:
50 parts of silyl-terminated polyethers
3～30 parts of reactive thinners
10～70 parts of fillers
5～30 parts of strengthening agents
0.1～5 part of moisture content scavenging agent
0.1～5 part of adhesive accelerant
0.1～2 part of curing catalyst.
2. a kind of environment-friendly type silyl-terminated polyether seal gum according to claim 1 is characterized in that, comprises the raw material of following weight part:
50 parts of silyl-terminated polyethers
3～15 parts of reactive thinners
10～40 parts of fillers
5～20 parts of strengthening agents
0.1～2.5 part of moisture content scavenging agent
0.1～5 part of adhesive accelerant
0.1～2 part of curing catalyst.
3. a kind of environment-friendly type silyl-terminated polyether seal gum according to claim 1 is characterized in that, comprises the raw material of following weight part:
50 parts of silyl-terminated polyethers
15～30 parts of reactive thinners
40～70 parts of fillers
20～30 parts of strengthening agents
2.5～5 parts of moisture content scavenging agents
0.1～5 part of adhesive accelerant
0.1～2 part of curing catalyst.
4. according to each described a kind of environment-friendly type silyl-terminated polyether seal gum in the claim 1 to 3, it is characterized in that: described silyl-terminated polyether comprise in the polyoxytrimethylene ether of the polyoxytrimethylene ether of polyoxytrimethylene ether, terminal methyl diethoxy silyl polyoxytrimethylene ether, end triethoxysilyl of the polyoxytrimethylene ether of holding trimethoxysilyl, terminal methyl dimethoxy silyl and terminal methyl trimethoxysilyl any 2.
5. according to each described a kind of environment-friendly type silyl-terminated polyether seal gum in the claim 1 to 3, it is characterized in that: described reactive thinner be molecular weight less than 1500, end group is the polyoxytrimethylene ether of hydrolyzable silane base.
6. a kind of environment-friendly type silyl-terminated polyether seal gum according to claim 5 is characterized in that: described hydrolyzable silane base be in dimethylmethoxysilylgroups groups and the dimethyl (ethoxymethyl) silylation any 2.
7. according to each described a kind of environment-friendly type silyl-terminated polyether seal gum in the claim 1 to 3, it is characterized in that: described filler be Paris white, talcum powder, through the Paris white of surface modification and in the wollastonite powder any or several; Described strengthening agent is carbon black or white carbon black; Described moisture content scavenging agent is the silane coupling agent or the oxazole alkanes moisture content scavenging agent of the reaction that easily is hydrolyzed.
8. according to each described a kind of environment-friendly type silyl-terminated polyether seal gum in the claim 1 to 3, it is characterized in that: described adhesive accelerant be in gamma-mercaptopropyltriethoxysilane, γ-An Bingjisanjiayangjiguiwan, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-methacryloxypropyl trimethoxy silane and γ-glycidyl ether oxygen base propyl trimethoxy silicane any or several.
9. according to each described a kind of environment-friendly type silyl-terminated polyether seal gum in the claim 1 to 3, it is characterized in that: described curing catalyst be in compound accelerant, dibutyl tin laurate and the modification organotin catalysts of organo-tin compound and alkylamine any or several.
10. the preparation method of each described a kind of environment-friendly type silyl-terminated polyether seal gum in the claim 1 to 3 is characterized in that, comprising:
Press formula ratio successively will, silyl-terminated polyether, reactive thinner, filler and strengthening agent join in the stirring tank, under 60～100 ℃, the condition of exsiccant protection of inert gas, mix and stir 1～4h; Be cooled to below 40 ℃, add moisture content scavenging agent, adhesive accelerant, curing catalyst again, under vacuum condition, stir 15～30min, obtain environment-friendly type silyl-terminated polyether seal gum.
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Address after: 523000 Guangdong city of Dongguan province Guangdong Town Village nine Pu Saida sealing adhesive Co. Ltd Patentee after: GUANGDONG PUSTAR SEALING ADHESIVE CO., LTD. Address before: 523000 Guangdong city of Dongguan Province town third Jinlong Industrial Zone Dongguan pustar sealing adhesive Co. Ltd Patentee before: Dongguan Pustar Adhesives & Sealants Co., Ltd. |