CN111574930A - Silane modified polyether sealant and preparation method thereof - Google Patents
Silane modified polyether sealant and preparation method thereof Download PDFInfo
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- CN111574930A CN111574930A CN202010288575.3A CN202010288575A CN111574930A CN 111574930 A CN111574930 A CN 111574930A CN 202010288575 A CN202010288575 A CN 202010288575A CN 111574930 A CN111574930 A CN 111574930A
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- 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
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
The invention provides a silane modified polyether sealant and a preparation method thereof, wherein the silane modified polyether sealant comprises the following raw materials in percentage by weight: 20-40% of silane modified polyether resin, 8-20% of plasticizer, 10-36% of nano filler, 10-30% of incremental filler, 0.1-5% of functional filler, 0.1-3% of thixotropic agent, 0.1-1% of ultraviolet absorbent, 0.1-1% of light stabilizer, 0.1-3% of antioxidant, 0-0.5% of water removing agent, 0.1-4% of adhesion promoter and 0.05-2% of catalyst, wherein the silane modified polyether resin is acrylic resin modified methyldimethoxysilane terminated polyether. The silane modified polyether resin adopted by the invention is acrylic resin modified methyl dimethoxy silane terminated polyether, and compared with silane modified polyether resin in the prior art, an acrylate structure similar to the structure of a PP material is added, so that the silane modified polyether resin and the surface of the PP material have better adhesion performance.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a silane modified polyether sealant and a preparation method thereof.
Background
Along with the improvement of the automobile manufacturing technology level and the functional requirements of customers on the economy, comfort, light weight and the like of the automobile, the sealant product is more and more widely applied to the manufacturing of passenger cars. Due to the requirement of light weight, more and more functional plastic materials, such as PP plastics, are used in the finished vehicle manufacturing process. The PP plastic is a semi-crystalline thermoplastic plastic, and has high impact resistance, mechanical properties and solvent resistance. Meanwhile, the PP plastic has the structural characteristics of low surface energy and poor wetting ability, so that the connection treatment of the PP plastic substrate has a great problem. The conventional connecting method comprises the steps of carrying out plasma treatment on the surface of a PP plastic product or adopting a PP priming coating treatment agent for treatment and then adopting adhesion besides plastic welding. The connection process is complicated and has high requirements on equipment. Therefore, how to improve the bottomless coating adhesion of the adhesive to the PP plastic is a problem which always troubles the material technical personnel.
The silane modified polyether sealant is a high-performance environment-friendly sealant prepared by taking silyl-terminated polyether as a basic polymer, has excellent mechanical strength, coating property and stain resistance, is free from perchlorate and organic solvent in the product, and is the main development direction of novel elastic sealants at home and abroad. CN110105907A adopts a mixture of two methyldimethoxysilane modified polyethers with different reaction activities and trimethoxy silane modified polyether as silane modified polyester resin, and combines a certain plasticizer, filler, thixotropic agent and other auxiliary agents to prepare the single-component silane modified polyether sealant for automobile glass, which has stronger initial bonding strength and has the function of rapid bonding and positioning. CN108753233A is used for matching dimethoxy silane terminated polyether with viscosity of 10-80 Pa.s with reinforcing carbon black and an incremental filler, and is cooperated with a curing accelerator, an adhesion promoter and other components, so that the single-component high-performance silane modified polyether sealant with high strength, high elongation, high shear strength, good environmental protection and excellent no-primer adhesion performance can be obtained. However, the existing silane modified polyether sealant is still weak in bonding strength to PP materials and cannot effectively bond PP materials.
Disclosure of Invention
The invention aims to provide a silane modified polyether sealant which has strong bonding strength to a PP material and can effectively bond the PP material.
The silane modified polyether sealant provided by the invention comprises the following raw materials in percentage by weight:
20-40% of silane modified polyether resin;
8 to 20 percent of plasticizer;
10 to 36 percent of nano filler;
10 to 30 percent of incremental filler;
0.1 to 5 percent of functional filler;
0.1 to 3 percent of thixotropic agent;
0.1 to 1 percent of ultraviolet absorbent;
0.1 to 1 percent of light stabilizer;
0.1 to 3 percent of antioxidant;
0 to 0.5 percent of water removing agent;
0.1 to 4 percent of adhesion promoter;
0.05 to 2 percent of catalyst;
the silane modified polyether resin is acrylic resin modified methyl dimethoxy silane terminated polyether.
Furthermore, the viscosity of the acrylic resin modified methyldimethoxysilane terminated polyether is 30000 mPa.s-80000 mPa.s (room temperature).
Further, the adhesion promoter is prepared by compounding modified polybutadiene and a silane coupling agent.
Further, the mass ratio of the modified polybutadiene to the silane coupling agent is (2-4): 1.
Further, the modified polybutadiene is selected from maleic anhydride modified polybutadiene, and the viscosity is 25000 mPa.s-60000 mPa.s.
Further, the silane coupling agent is selected from a mixture of an acryloyloxysilane and an aminosilane.
Furthermore, the mass ratio of the acryloyloxysilane to the aminosilane is 1 (2-5).
Further, the acryloyloxysilane is at least one selected from the group consisting of 3- (acryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (acryloyloxy) methyldimethoxysilane and 3- (methacryloyloxy) propyltriisopropoxysilane.
Further, the aminosilane is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
Further, the plasticizer is at least one of environment-friendly plasticizers such as alkyl phenyl sulfonate, polypropylene glycol 2000, polypropylene glycol 3000, cyclohexane 1, 2-dicarboxylic acid diisononyl ester and the like.
Furthermore, the nano filler is active nano calcium carbonate, and the particle size of the nano filler is 60 nm-80 nm.
Furthermore, the incremental filler is active heavy calcium carbonate, and the mesh number of the incremental filler is 800-1300 meshes.
Further, the functional material is a composite material formed by mixing nano activated carbon, carbonate, silicate, photocatalyst and heat activated catalyst.
Furthermore, the ratio of the total mass of the nano activated carbon, the carbonate and the silicate to the total mass of the photocatalyst and the thermal activation catalyst is (3-4): 1.
Further, the thixotropic agent is selected from a polyamide wax and/or fumed silica.
Further, the ultraviolet absorber is selected from the group consisting of 2- (2 '-hydroxy-3', 5 '-di-tert-amylphenyl) benzotriazole (Tinuvin 328), 2- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (Tinuvin 326), 2- (2 '-hydroxy-5' -methylphenyl) -benzotriazole (UV-P), 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) -5-chlorobenzotriazole (Tinuvin 327), 2- (2' -hydroxy-5 '-tert-butylphenyl) -benzotriazole (Tinuvin 5411) and 2-2' -methylene- (6- (2H-benzotriazole) -4-tert-octyl) phenol (Tinuvin 5431) At least one of them.
Further, the light stabilizer is at least one selected from poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate (Tinuvin622), bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770), bis 1-octyloxy-2, 2,6, 6-tetramethylpiperidinol sebacate (Tinuvin 523).
Further, the antioxidant is selected from pentaerythritol beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox1010), octadecyl 3, 5-di-tert-butyl-4-hydroxyphenyl propionate (Irganox 1076), N-bis- [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -1, 6-hexanediamine (Irganox 1098), triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Irganox 245), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) 1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione (Irganox3114), tris (2, 4-di-tert-butylphenyl) phosphite (Irgafos 168), bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite (Irgafos 126) and lauryl 3, 3-thiopropionate (DLTDP).
Further, the water scavenger is selected from at least one of vinyltrimethoxysilane, vinyltriethoxysilane and vinyldimethoxysilane.
Further, the catalyst is an organotin catalyst; in some embodiments, the organotin catalyst is dibutyltin bis (acetylacetonate).
The invention also provides a preparation method of the silane modified polyether sealant, which comprises the following steps:
(1) mixing silane modified polyether resin, a plasticizer, a thixotropic agent, a nano filler, an incremental filler, a functional filler, an ultraviolet absorbent, a light stabilizer and an antioxidant, dispersing at a high speed for 20-30 min, and stirring at the temperature of-0.09 MPa to-0.1 MPa and the material temperature of 110-120 ℃ for 120-180 min;
(2) cooling to 50 ℃ or below, adding a water removing agent, an adhesion promoter and a catalyst, uniformly dispersing, continuously stirring for 20-40 min under the condition that the vacuum degree is-0.09 MPa to-0.1 MPa, and discharging to obtain the water-based paint.
Further, before the step (1), the nano filler and the incremental filler are pre-dried for 10-20 hours at the temperature of 130-150 ℃.
The silane modified polyether resin adopted by the invention is acrylic resin modified methyl dimethoxy silane terminated polyether, and compared with methyl dimethoxy silane modified polyether, trimethoxy silane modified polyether or dimethoxy silane terminated polyether resin in the prior art, the acrylate structure similar to the polyolefin structure in the PP material is added, so that the silane modified polyether resin and the PP material surface have better adhesion performance; the viscosity of the acrylic resin modified methyldimethoxysilane terminated polyether is preferably 30000 mPa.s-80000 mPa.s, so that the bonding strength of the silane modified polyether resin and the surface of the PP material can be maximized; meanwhile, the adhesion promoter compounded by liquid polybutadiene and a silane coupling agent (especially acryloyloxy silane) is adopted to improve the wetting effect of the silane modified polyether resin on the surface of the PP material, and further improve the adhesion effect of the silane modified polyether sealant on the PP material.
The invention has the following technical effects:
(1) the shear strength of the silane modified polyether sealant is as high as 0.79-1.05 MPa, the peel strength is as high as 3.8-4.8 KN/m, and compared with the silane modified polyether sealant which takes methyldimethoxysilane modified polyether as a base polymer and takes silane coupling agent or modified polybutadiene as an adhesion promoter, the silane modified polyether sealant is improved by more than 2 times;
(2) the silane modified polyether sealant disclosed by the invention has an excellent adhesion effect on the surface of a PP (polypropylene) material and is difficult to peel.
Drawings
FIG. 1 shows the peeling of the silane modified polyether sealant of examples 1 to 4 from the surface of a PP material;
FIG. 2 shows the peeling of the silane modified polyether sealant of comparative examples 1 to 3 from the surface of a PP material.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1
A single-component silane modified polyether sealant for PP material bonding comprises the following raw materials:
note: the functional materials described in examples 1 to 4 and comparative examples 1 to 5 are composite materials formed by mixing nano activated carbon, carbonate, silicate, photocatalyst and heat activated catalyst, and the ratio of the total mass of the nano activated carbon, the carbonate and the silicate to the total mass of the photocatalyst and the heat activated catalyst is 3.3: 1.
The preparation method comprises the following steps:
(1) pre-drying the active nano calcium carbonate and the active heavy calcium carbonate for 12 hours at the temperature of 140 ℃ for later use.
(2) Adding MAX602, cyclohexane 1, 2-diisononyl phthalate, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, functional filler, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 20min at a high speed; then stirring for 120min under the conditions that the vacuum degree is-0.09 MPa and the material temperature is 110 ℃;
(3) cooling to 50 ℃, sequentially adding a proper amount of vinyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, 3- (acryloyloxy) propyltrimethoxysilane, modified polybutadiene and dibutyltin bis (acetyl acetonate), uniformly dispersing, continuously stirring for 30min under the condition that the vacuum degree is-0.09 MPa, and discharging to obtain the nano-composite material.
Example 2
A single-component silane modified polyether sealant for PP material bonding comprises the following raw materials:
the preparation method comprises the following steps:
(1) pre-drying active nano calcium carbonate and active heavy calcium carbonate for 12 hours at the temperature of 140 ℃ for later use;
(2) adding MAX480, alkyl phenyl sulfonate, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, a functional filler, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 20min at a high speed; then stirring for 120min under the conditions that the vacuum degree is-0.09 MPa and the material temperature is 110 ℃.
(3) Cooling to 50 ℃, sequentially adding a proper amount of vinyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3- (acryloyloxy) methyldimethoxysilane, modified polybutadiene and dibutyltin bis (acetyl acetonate), uniformly dispersing, continuously stirring for 30min under the condition that the vacuum degree is-0.09 MPa, and discharging to obtain the nano-composite material.
Example 3
A single-component silane modified polyether sealant for PP material bonding comprises the following raw materials:
the preparation method comprises the following steps:
(1) pre-drying the active nano calcium carbonate and the active heavy calcium carbonate for 12 hours at the temperature of 150 ℃ for later use.
(2) Adding MAX951, polypropylene glycol 2000, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, a functional filler, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 20-30 min at a high speed; then stirring for 180min under the conditions that the vacuum degree is-0.1 MPa and the material temperature is 120 ℃.
(3) Cooling to 50 ℃, sequentially adding a proper amount of vinyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3- (acryloyloxy) methyldimethoxysilane, modified polybutadiene and dibutyltin bis (acetyl acetonate), uniformly dispersing, continuously stirring for 30min under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the nano-composite material.
Example 4
A single-component silane modified polyether sealant for PP material bonding comprises the following raw materials:
the preparation method comprises the following steps:
(1) pre-drying the active nano calcium carbonate and the active heavy calcium carbonate for 12 hours at the temperature of 130 ℃ for later use.
(2) Adding MAX951, polypropylene glycol 2000, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, a functional filler, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 20-30 min at a high speed; then stirring for 120min under the conditions that the vacuum degree is-0.1 MPa and the material temperature is 120 ℃.
(3) Cooling to 50 ℃, sequentially adding a proper amount of vinyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3- (acryloyloxy) methyldimethoxysilane, modified polybutadiene and dibutyltin bis (acetyl acetonate), uniformly dispersing, continuously stirring for 30min under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the nano-composite material.
Comparative example 1
In the silane modified polyether sealant of the comparative example, the acrylic resin modified methyldimethoxysilane terminated polyether is replaced by the methyldimethoxysilane modified polyether, and the modified polybutadiene in the adhesion promoter is saved, wherein the specific raw materials are shown in the following table:
the preparation method comprises the following steps:
(1) drying the active nano calcium carbonate and the active heavy calcium carbonate at 130 ℃ for 12h for later use.
(2) Adding S303H, polypropylene glycol 2000, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 30min at a high speed; then stirring for 180min under the conditions that the vacuum degree is-0.09 MPa and the material temperature is 120 ℃.
(3) Cooling to 50 deg.C, sequentially adding appropriate amount of vinyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3- (acryloyloxy) methyldimethoxysilane and dibutyltin bis (acetyl acetonate), dispersing uniformly, stirring under vacuum degree of-0.1 MPa for 30min, and discharging.
Comparative example 2
In the silane modified polyether sealant of the comparative example, the acrylic resin modified methyldimethoxysilane terminated polyether is replaced by the methyldimethoxysilane modified polyether, and the modified polybutadiene and the acryloxysilane in the adhesion promoter are saved, and the specific raw materials are shown in the following table:
the preparation method comprises the following steps:
(1) drying the active nano calcium carbonate and the active heavy calcium carbonate at 130 ℃ for 12h for later use.
(2) Adding S303H, cyclohexane 1, 2-diisononyl phthalate, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 20-30 min at a high speed; then stirring for 120min under the conditions that the vacuum degree is-0.1 MPa and the material temperature is 120 ℃.
(3) Cooling to 50 deg.C, sequentially adding appropriate amount of vinyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and dibutyltin bis (acetyl acetonate), dispersing uniformly, stirring under vacuum degree of-0.1 MPa for 30min, and discharging.
Comparative example 3
In the silane modified polyether sealant of the comparative example, the acrylic resin modified methyldimethoxysilane terminated polyether is replaced by the methyldimethoxysilane modified polyether, and aminosilane and acryloxysilane in the adhesion promoter are saved, wherein the specific raw materials are shown in the following table:
the preparation method comprises the following steps:
(1) drying the active nano calcium carbonate and the active heavy calcium carbonate at 130 ℃ for 12h for later use.
(2) Adding S303H, cyclohexane 1, 2-diisononyl phthalate, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, functional filler, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 20min at a high speed; then stirring for 180min under the conditions that the vacuum degree is-0.1 MPa and the material temperature is 120 ℃.
(3) Cooling to 50 ℃, sequentially adding a proper amount of vinyltrimethoxysilane, modified polybutadiene and dibutyltin bis (acetylacetonate), uniformly dispersing, continuously stirring for 30min under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the modified polybutadiene.
Comparative example 4
In the silane modified polyether sealant of the comparative example, the acrylic resin modified methyldimethoxysilane terminated polyether is replaced by the methyldimethoxysilane modified polyether in the aspect of raw material selection, and the specific raw materials are shown in the following table:
the preparation method comprises the following steps:
(1) pre-drying the active nano calcium carbonate and the active heavy calcium carbonate for 12 hours at the temperature of 130 ℃ for later use.
(2) Adding S303H, polypropylene glycol 2000, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, a functional filler, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 20-30 min at a high speed; then stirring for 120min under the conditions that the vacuum degree is-0.1 MPa and the material temperature is 120 ℃.
(3) Cooling to 50 ℃, sequentially adding a proper amount of vinyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3- (acryloyloxy) methyldimethoxysilane, modified polybutadiene and dibutyltin bis (acetyl acetonate), uniformly dispersing, continuously stirring for 30min under the condition that the vacuum degree is-0.1 MPa, and discharging to obtain the nano-composite material.
Comparative example 5
The silane modified polyether sealant of the comparative example omits modified polybutadiene in the adhesion promoter in terms of raw material selection, and the specific raw materials are shown in the following table:
the preparation method comprises the following steps:
(1) drying the active nano calcium carbonate and the active heavy calcium carbonate at 130 ℃ for 12h for later use.
(2) Adding MAX602, cyclohexane 1, 2-diisononyl phthalate, polyamide wax, active nano calcium carbonate, active heavy calcium carbonate, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacic acid ester and triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate into a planetary kettle in sequence, and dispersing for 20-30 min at a high speed; then stirring for 120min under the conditions that the vacuum degree is-0.1 MPa and the material temperature is 120 ℃.
(3) Cooling to 50 deg.C, sequentially adding appropriate amount of vinyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3- (acryloyloxy) methyldimethoxysilane and dibutyltin bis (acetyl acetonate), dispersing uniformly, stirring under vacuum degree of-0.1 MPa for 30min, and discharging.
And (3) carrying out performance test on each silane modified polyether sealant, wherein the test method comprises the following steps: (1) the testing method of the sealant TVOC comprises the following steps: reference VDA 277; (2) the method for testing the shear strength of the sealant comprises the following steps: reference GB/T7124-2008 (adhesive thickness 4 mm); (3) the test method of the peeling adhesiveness of the sealant comprises the following steps: reference GB/T13477.18; (4) test method of hand-peel adhesion: refer to method B of D.1.2 in appendix D of GB 16776-.
The test results are shown in the following table:
as can be seen from the table above, the silane modified polyether sealant prepared by using the methyldimethoxysilane modified polyether as the base polymer and adjusting the composition of the adhesion promoter in the comparative examples 1-4 has the shear strength of only 0.05-0.3 MPa and the peel strength of only 0.25-1.4 KN/m; meanwhile, the acrylic resin modified methyldimethoxysilane terminated polyether is independently adopted as the basic polymer, the shearing strength of the silane modified polyether sealant prepared by omitting the polybutadiene component is 0.4MPa, and the peeling strength is 2.5 KN/m. According to the invention, the base polymer is replaced by acrylic resin modified methyldimethoxysilane terminated polyether, and the compound system of modified polybutadiene and silane coupling agent is used as the adhesion promoter, so that the shear strength of the obtained silane modified polyether sealant is improved to 0.79-1.05 MPa, and the peel strength is improved to 3.8-4.8 KN/m, which is improved by 2 times or more compared with comparative examples 1-5. Therefore, the base polymer taking the acrylic resin modified methyldimethoxysilane terminated polyether as the sealant can effectively improve the bonding property between the sealant and the PP material, and the compound system of the modified polybutadiene and the silane coupling agent can effectively improve the wetting effect between the sealant and the PP material surface.
In addition, the silane modified polyether sealants of the examples 1 to 4 and the comparative examples 1 to 3 are coated on the surface of a PP material, the peeling adhesion of the silane modified polyether sealant on the surface of the PP material is tested after the PP material is maintained for 7 days under standard conditions, and the peeling condition of the silane modified polyether sealant on the surface of the PP material is shown in figures 1 and 2, wherein a to d in figure 1 sequentially represent the silane modified polyether sealants of the examples 1 to 4, and a to c in figure 2 sequentially represent the silane modified polyether sealants of the comparative examples 1 to 3. As can be seen from FIGS. 1 and 2, the silane modified polyether sealants of examples 1 to 4 are firmly adhered to the surface of PP material and are difficult to peel off, while the silane modified polyether sealants of comparative examples 1 to 3 are easily peeled off from the surface of PP material and cannot be effectively adhered.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A silane modified polyether sealant is characterized in that: comprises the following raw materials in percentage by weight:
20-40% of silane modified polyether resin;
8 to 20 percent of plasticizer;
10 to 36 percent of nano filler;
10 to 30 percent of incremental filler;
0.1 to 5 percent of functional filler;
0.1 to 3 percent of thixotropic agent;
0.1 to 1 percent of ultraviolet absorbent;
0.1 to 1 percent of light stabilizer;
0.1 to 3 percent of antioxidant;
0 to 0.5 percent of water removing agent;
0.1 to 4 percent of adhesion promoter;
0.05 to 2 percent of catalyst;
the silane modified polyether resin is selected from acrylic resin modified methyl dimethoxy silane terminated polyether.
2. The silane-modified polyether sealant according to claim 1, wherein: the room temperature viscosity of the acrylic resin modified methyl dimethoxy silane terminated polyether is 30000 mPa.s-80000 mPa.s.
3. The silane-modified polyether sealant according to claim 1, wherein: the adhesion promoter is prepared by compounding modified polybutadiene and a silane coupling agent.
4. The silane-modified polyether sealant according to claim 3, wherein: the mass ratio of the modified polybutadiene to the silane coupling agent is (2-4) to 1.
5. The silane-modified polyether sealant according to claim 3, wherein: the modified polybutadiene is selected from maleic anhydride modified polybutadiene, and the viscosity of the modified polybutadiene is 25000 mPa.s-60000 mPa.s.
6. The silane-modified polyether sealant according to claim 3, wherein: the silane coupling agent is selected from a mixture of an acryloyloxysilane and an aminosilane.
7. The silane-modified polyether sealant according to claim 6, wherein: the mass ratio of the acryloyloxysilane to the aminosilane is 1 (2-5).
8. The silane-modified polyether sealant according to claim 6, wherein: the acryloxysilane is at least one selected from 3- (acryloxy) propyltrimethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3- (acryloxy) methyldimethoxysilane and 3- (methacryloxy) propyltriisopropoxysilane; the aminosilane is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
9. The process for preparing a silane-modified polyether sealant according to any one of claims 1 to 8, wherein: the method comprises the following steps: (1) mixing silane modified polyether resin, a plasticizer, a thixotropic agent, a nano filler, an incremental filler, a functional filler, an ultraviolet absorbent, a light stabilizer and an antioxidant, dispersing at a high speed for 20-30 min, and stirring at the temperature of-0.09 MPa to-0.1 MPa and the material temperature of 110-120 ℃ for 120-180 min;
(2) cooling to 50 ℃ or below, adding a water removing agent, an adhesion promoter and a catalyst, uniformly dispersing, continuously stirring for 20-40 min under the condition that the vacuum degree is-0.09 MPa to-0.1 MPa, and discharging to obtain the water-based paint.
10. The method of claim 9, wherein: before the step (1), pre-drying the nano filler and the incremental filler for 10-20 hours at the temperature of 130-150 ℃.
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