CN113337008A - Two-component tackifier, liquid silicone rubber and preparation method thereof - Google Patents

Two-component tackifier, liquid silicone rubber and preparation method thereof Download PDF

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CN113337008A
CN113337008A CN202110647165.8A CN202110647165A CN113337008A CN 113337008 A CN113337008 A CN 113337008A CN 202110647165 A CN202110647165 A CN 202110647165A CN 113337008 A CN113337008 A CN 113337008A
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tackifier
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张霆宇
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/08—Macromolecular additives
    • 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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  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a two-component tackifier, which comprises an A-type tackifier and a B-type tackifier, wherein the A-type tackifier has the following structure:
Figure DDA0003109534580000011
wherein m + n is 30-100, m is greater than or equal to 3, and n is greater than or equal to 2; the X is an alkyl group with a functional group, and the carbon number of the alkyl group is more than or equal to 2; the B-type tackifier has the following structure:

Description

Two-component tackifier, liquid silicone rubber and preparation method thereof
Technical Field
The invention relates to the field of adhesives, in particular to a two-component tackifier, liquid silicone rubber and a preparation method thereof.
Background
Liquid silicone rubber currently has good bonding capability for bonding between metals, such as silver and copper, but due to the inherent properties of the liquid silicone rubber structure, when used for bonding between plastics, the bonding performance is poor, such as PC, PBT, PA6 and ABS, and functional groups or polar groups are usually introduced into the liquid silicone rubber system to increase the bonding force, such as alkoxy silicon groups, epoxy groups, phenyl groups and alkoxy groups.
The prior art discloses a part of the bonding for PC and polyamide, for example, Chinese invention patent with publication number CN112111222A discloses a two-component addition type silicone rubber for a priming-free polyamide substrate and a preparation scheme thereof, wherein the A component comprises the following components by mass percent: 60-80% of vinyl polysiloxane; 10-20% of fumed silica and 0.1-1% of platinum catalyst; 0.2-1.5% of vinyl trimethoxy silane; the component B comprises the following components in percentage by mass: 60-80% of vinyl polysiloxane; 10-20% of fumed silica; 5-15% of low hydrogen-containing polysiloxane; 0.1-0.5% of inhibitor; 0.2-1.5% of vinyl triethoxysilane, and through the blending of the components and the proportion, the adhesive force between polyamide substrates can be increased to a certain extent, and the use of a primer is avoided.
Similarly, the chinese patent publication No. CN111793365A discloses a silicone rubber for polyamide, which comprises a certain proportion of vinyl polysiloxane, polydimethylsiloxane, fumed silica, hexamethyldisilazane, tetramethyldivinyldisilazane, distilled water, terminal hydrogen-containing silicone oil or side hydrogen-containing silicone oil, an inhibitor and an adhesive with a specific structure, and realizes the adhesion of polyamide substrates, but the adhesion strength is not ideal.
Also, the Chinese invention patent with the publication number of CN105131291B discloses a tackifier with the structural formula of CH and a preparation method thereof, and liquid silicone rubber containing the tackifier and a preparation method thereof3-C(＝CH2)-C(＝O)-O-(CH2)3-Si(OCH3)2-(SiO(CH3)2)m-(SiO(H,CH3))n-Si(OCH3)-(CH2)3-O-CH2-(CH2OCH2) Although m + n is 15 to 20, the liquid silicone rubber containing the tackifier is not preferable in terms of adhesion strength to PA, cohesive failure is not achieved, and adhesion strength to ABS is not preferable.
Therefore, it is necessary to provide a new tackifier to solve the above problems, and to provide a method for preparing the above tackifier, and further to provide a liquid silicone rubber comprising the above tackifier.
Disclosure of Invention
The first purpose of the invention is to provide a two-component tackifier to solve the defects in the background technology.
In order to achieve the purpose, the invention provides a two-component tackifier which is characterized by comprising an A-type tackifier and a B-type tackifier, wherein the A-type tackifier has the following structure:
Figure BDA0003109534570000021
wherein m + n is 30-100, m is greater than or equal to 3, and n is greater than or equal to 2;
the X is an alkyl group with a functional group, and the carbon number of the alkyl group is more than or equal to 2;
the B-type tackifier has the following structure:
Figure BDA0003109534570000031
wherein, the R1 is an alkyl group with a functional group, when the R3 is a hydrogen group, the R2 is an alkyl group with a functional group, when the R3 is an alkyl group with a functional group, the R2 is a hydrogen group or an alkyl group with a functional group, and the carbon number of the alkyl group in the R1, the R2 and the R3 is more than or equal to 2.
Preferably, m + n is 30 to 70.
Preferably, said m is from 10 to 40 and/or said n is from 4 to 10.
Preferably, the functional group in X includes one of phenyl, cycloalkyl or a combination of both.
The second purpose of the invention is to provide a preparation method of the two-component tackifier, which is used for preparing the two-component tackifier and comprises the following steps:
preparation of a type A tackifier:
mixing trimethyl end-capped straight-chain type hydrogen-containing silicone oil with the polymerization degree of 30-100 with an organic solvent, pouring the mixture into a first multi-neck round-bottom flask with a mechanical stirring thermometer, stirring and heating to 70-80 ℃, and stabilizing for 30 +/-10 min to obtain a straight-chain type hydrogen-containing silicone oil system, wherein the amount of the olefin monomer A with the functional group is 2-98 times that of the trimethyl end-capped straight-chain type hydrogen-containing silicone oil;
exhausting air in the first multi-mouth round-bottom flask by using inert gas;
mixing a chloroplatinic acid catalytic system and an olefin monomer A with a functional group to obtain a first drop of feed containing a catalyst, wherein the chloroplatinic acid is 5-10 ppm;
under the protection of inert gas, carrying out constant pressure titration on the straight-chain type hydrogen-containing silicone oil system by the first drop of feeding, wherein the titration time is 15-60min, after the titration is finished, continuously reacting for 1-2H at 80-100 ℃, and removing the organic solvent by rotary evaporation to obtain the A-type tackifier;
preparation of B-type tackifier:
mixing 1, 3, 5, 7-tetramethylcyclotetrasiloxane and an organic solvent, pouring the mixture into a second multi-mouth round-bottom flask with a mechanical stirring thermometer, stirring and heating to 70-80 ℃, and stabilizing for 30 +/-10 min to obtain a hydrogen-containing cyclic silicone oil system, wherein the amount of the substance of the olefin monomer B with the functional group is 2-3.9 times of that of the 1, 3, 5, 7-tetramethylcyclotetrasiloxane;
exhausting air in the second multi-mouth round-bottom flask by using inert gas;
mixing a chloroplatinic acid catalytic system and an olefin monomer B with a functional group to obtain a second drop charge containing a catalyst, wherein the chloroplatinic acid is 5-10 ppm;
under the protection of inert gas, carrying out constant pressure titration on the hydrogen-containing annular silicone oil system by using the second dropwise adding material, wherein the titration time is 15-60min, after the titration is finished, continuously reacting for 1-2H at 80-100 ℃, and removing the organic solvent by rotary evaporation to obtain the B-type tackifier.
In the preparation of A class tackifier and B class tackifier, organic solvent includes toluene, and organic solvent plays the effect of dissolving, and organic solvent's specific selection does not influence the performance of two ingredient tackifiers, inert gas includes nitrogen gas, and inert gas plays the guard action, inert gas's specific selection does not influence the performance of two ingredient tackifiers, and above-mentioned reaction is the addition reaction of the silicon hydrogen bond of chloroplatinic acid system catalysis and vinyl, according to the volume of the material of functional group just can be confirmed to the number that hydrogen was substituted in the straight-chain type hydrogen-containing silicone oil of trimethyl end-capping.
The functional group includes cycloalkyl groups and functional groups such as phenyl groups, alkoxy groups, ether groups, and siloxy groups.
The third purpose of the invention is to provide a liquid silicone rubber which is characterized by comprising any one of the two-component tackifier, wherein the mass part of the A-type tackifier is more than or equal to 0.5 part, the mass part of the B-type tackifier is more than or equal to 0.4 part, and the two-component tackifier also comprises the following components in parts by mass:
Figure BDA0003109534570000051
the silicon rubber further comprises a platinum catalyst, the concentration of the platinum catalyst is 10-40ppm, and the mass ratio of Si-H to vinyl in the liquid silicon rubber is 1.5-3.0; the liquid silicone rubber base rubber comprises the following components in parts by mass:
Figure BDA0003109534570000052
preferably, the mass part of the A-type tackifier is 0.5-3.0 parts and/or the mass part of the B-type tackifier is 0.4-3.0 parts.
Preferably, the reinforcing filler comprises one or a combination of three of white carbon black, diatomite and quartz powder, and the white carbon black comprises one or a combination of two of precipitated white carbon black and fumed white carbon black.
Preferably, the reinforcing filler has a specific surface area greater than or equal to 200m2/g。
Compared with the prior art, the invention has the beneficial effects that: (1) the two-component tackifier for the liquid silicone rubber comprises a straight-chain type A tackifier and a cyclic structure type B tackifier, and the two-component tackifier can be used for realizing bonding while forming and cohesive failure without any treatment on a base material when the liquid silicone rubber comprising the two-component tackifier is used for bonding plastics;
(2) the preparation method of the two-component tackifier is provided, and the method is simple and easy to operate;
(3) the specific composition of the liquid silicone rubber containing the two-component tackifier is provided, and the obtained liquid silicone rubber has good adhesive capacity to plastics, particularly PC, PBT, PA6 and ABS, and can achieve cohesive failure.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention and are not to be construed as limiting the scope of the present invention, and all equivalent changes and modifications according to the spirit of the present invention should be covered by the scope of the present invention.
In addition, the descriptions related to "first", "second", etc. in the present invention are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Example 1:
the two-component tackifier is characterized by comprising an A-type tackifier and a B-type tackifier, wherein the A-type tackifier comprises the following structures:
Figure BDA0003109534570000071
the adhesive is characterized in that m + n is 30-100, m is greater than or equal to 3, such as 35, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, n is greater than or equal to 2, such as 3, 5, 7, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, X is an alkyl group with a functional group, such as an alkyl group with an epoxy group, a phenyl group, an ether group, a cycloalkyl group and a siloxane group, the carbon number of the alkyl group is greater than or equal to 2, the functional group in X is one or a combination of two of phenyl and cycloalkyl, and the adhesive performance of the liquid silicone rubber with a benzene ring or cycloalkyl is better.
When the m + n is 30-70, the good adhesion can be ensured, and the material can be prevented from being too brittle.
In addition, when m is 10-40 or n is 4-10, the good adhesion can be ensured, and the material can be prevented from being too brittle.
In addition, when m is 10-40 and n is 4-10, the good adhesion can be ensured, and the material can be prevented from being too brittle.
A specific structure of the group a tackifier of example 1 of the present invention is represented as follows, wherein m + n is 40, m is 30, n is 10, the value of n is contributed by the polymerization degree values of two kinds of repeating units, the polymerization degree of each repeating unit is 5, and X is an alkyl group having a phenyl group and an alkyl group having an epoxy group and an ether group:
Figure BDA0003109534570000081
the class B tackifier comprises the following structure:
Figure BDA0003109534570000082
wherein, the R1 is an alkyl group with a functional group, such as an alkyl group with an epoxy group, a phenyl group, an ether group, a cycloalkyl group, a siloxy group, when the R3 is a hydrogen group, the R2 is an alkyl group with a functional group, such as an alkyl group with an epoxy group, a phenyl group, an ether group, a cycloalkyl group, a siloxy group, when the R3 is an alkyl group with a functional group, such as an alkyl group with an epoxy group, a phenyl group, an ether group, a cycloalkyl group, a siloxy group, the R2 is a hydrogen group or an alkyl group with a functional group, such as an alkyl group with an epoxy group, a phenyl group, an ether group, a cycloalkyl group, a siloxy group, the carbon number of the alkyl group in the R1, the R2, the R3 is greater than or equal to 2.
With the above arrangement, the group B tackifier has a cyclic silicone structure, and the number of S — H is 1 or 2, and does not exceed 2, and thus after the arrangement, the group B tackifier mainly functions as an adhesive and does not perform a crosslinking function, the group a tackifier is designed according to adhesion between an interface layer and silicone rubber, and the group B tackifier is designed according to adhesion between a substrate and the interface layer, and thus cohesive failure of almost 100% can be achieved, and a specific structure of the group B tackifier of embodiment 1 of the present invention is shown as follows:
Figure BDA0003109534570000091
the specific structural formula of example 1 does not limit the scope of the present invention, and the present invention sets the tackifier mainly by polymerization degree and structural general formula, and the value of n + m is limited because when the value is less than 30, the tackifying effect is poor, and the value is more than 100, the obtained class a tackifier is difficult to migrate to the contact surface, and the adhesiveness is better when the functional group of X in the class a tackifier includes one or a combination of two of phenyl group and cycloalkyl group.
Also provides a preparation method of the two-component tackifier, which is used for preparing the two-component tackifier in the embodiment 1.
Example 2:
a preparation method of a two-component tackifier comprises the following steps:
preparation of a type A tackifier:
mixing trimethyl end-capped straight-chain type hydrogen-containing silicone oil with the polymerization degree of 30-100 with an organic solvent, pouring the mixture into a first multi-neck round-bottom flask with a mechanical stirring thermometer, stirring and heating to 70-80 ℃, and stabilizing for 30 +/-10 min to obtain a straight-chain type hydrogen-containing silicone oil system, wherein the amount of the olefin monomer A with the functional group is 2-98 times that of the trimethyl end-capped straight-chain type hydrogen-containing silicone oil;
exhausting air in the first multi-mouth round-bottom flask by using inert gas;
mixing a chloroplatinic acid catalytic system and an olefin monomer A with a functional group to obtain a first drop of feed containing a catalyst, wherein the chloroplatinic acid is 5-10 ppm;
under the protection of inert gas, carrying out constant pressure titration on the linear hydrogen-containing silicone oil system by using the first catalyst reaction monomer mixed system for 30min, after titration is finished, continuing to react for 1-2H at 80-100 ℃, and removing the organic solvent by rotary evaporation to obtain the A-type tackifier, such as a reaction system of 100g of trimethyl end-capped linear hydrogen-containing silicone oil with the polymerization degree of 40, 23g of alpha-methylstyrene, 22.3g of allyl glycidyl ether, 0.3g of 0.5% chloroplatinic acid toluene solution and 50g of toluene;
preparation of B-type tackifier:
mixing 1, 3, 5, 7-tetramethylcyclotetrasiloxane and an organic solvent, pouring the mixture into a second multi-mouth round-bottom flask with a mechanical stirring thermometer, stirring and heating to 70-80 ℃, and stabilizing for 30 +/-10 min to obtain a hydrogen-containing cyclic silicone oil system, wherein the amount of the substance of the olefin monomer B with the functional group is 2-3.9 times of that of the 1, 3, 5, 7-tetramethylcyclotetrasiloxane;
exhausting air in the second multi-mouth round-bottom flask by using inert gas;
mixing a chloroplatinic acid catalytic system and an olefin monomer B with a functional group to obtain a second drop charge containing a catalyst, wherein the chloroplatinic acid is 5-10 ppm;
under the protection of inert gas, the second dropwise adding material is subjected to constant pressure titration on the hydrogen-containing cyclic silicone oil system for 15-60min, after the titration is finished, the reaction is continued for 1-2H at 80-100 ℃, and the organic solvent is removed by rotary evaporation, so that the B-type tackifier can be obtained, for example, a reaction system of 80g of 1, 3, 5, 7-tetramethylcyclotetrasiloxane, 40g of toluene, 0.3g of 0.5% chloroplatinic acid toluene solution and 78.6g of alpha-methylstyrene.
In the preparation of the tackifier a and the tackifier B in example 2, the organic solvent comprises toluene, the selection of the organic solvent does not affect the performance of the tackifier a and the tackifier B, the specific selection of the organic solvent does not affect the scope of the invention, and in addition, the inert gas comprises nitrogen and plays a role in protection, and the specific selection of the inert gas does not affect the scope of the invention.
Wherein, a specific structure of the trimethyl end-capped linear hydrogen-containing silicone oil in the embodiment 2 is as follows:
Figure BDA0003109534570000111
the chemical structure of 1, 3, 5, 7-tetramethylcyclotetrasiloxane described in example 2 is as follows:
Figure BDA0003109534570000112
the principle of the above preparation method is an addition reaction of hydrosilation and vinyl groups, and a detailed mechanism is prior art, and thus, a detailed addition process is not described herein.
Example 2 is only a specific example, and a specific structure shown by the tackifier of group a and the tackifier of group B in example 1 is obtained, and the substitution of the vinyl monomer having a functional group and the adjustment of the polymerization degree are obtained, and other structures not specifically shown of the tackifier of group a in example 1 can be obtained by the method of example 2, and the substitution of the vinyl monomer having a functional group and the change of the number and position of hydrogen in the 1, 3, 5, 7-tetramethylcyclotetrasiloxane can be obtained by the method of example 2 to obtain other structures not specifically shown of the tackifier of group B in example 1.
In example 2, the theoretical amount of the substance of the olefin monomer a having a functional group can be determined by determining the degree of polymerization of the siloxy group in which the alkyl group having a functional group is present, but in the actual reaction, the reaction is incomplete, so that the amount of the substance of the olefin monomer a having a functional group is slightly higher than the theoretical amount, and similarly, the amount of the substance of the olefin monomer B having a functional group is slightly higher than the theoretical amount.
Also provides a liquid silicone rubber, which comprises the two-component tackifier of the embodiment.
Example 3:
a liquid silicone rubber comprises any one of the two-component tackifiers of the above embodiments, wherein the mass portion of the A-type tackifier is greater than or equal to 0.5 parts, the mass portion of the B-type tackifier is greater than or equal to 0.4 parts, and the liquid silicone rubber further comprises the following components in parts by mass:
Figure BDA0003109534570000121
further comprising a platinum group catalyst in a concentration of 10 to 40ppm, the liquid silicone rubber having a mass ratio of Si-H to vinyl of 1.5 to 3.0, for example, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8; the liquid silicone rubber base rubber comprises the following components in parts by mass:
Figure BDA0003109534570000122
preferably, the part by mass of the tackifier of group a is 0.5 to 3.0 parts, for example, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 2 parts, 2.5 parts and/or the part by mass of the tackifier of group B is 0.4 to 3.0 parts, for example, 0.5 part, 0.7 part, 0.9 part, 1.1 part, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, and as a further preferable, the part by mass of the tackifier of group a is 0.5 to 3.5 parts, and the part by mass of the tackifier of group B is 0.5 to 5.5 parts.
When the addition amount of the type A tackifier is less than 0.5 part and the addition amount of the type B tackifier is less than 0.4 part, the liquid silicone rubber has no adhesiveness, when the addition amount of the type A tackifier is more than 3 parts, and when the addition amount of the type B tackifier is more than 3 parts, the rubber material of the liquid silicone rubber is brittle;
further optimized, the reinforcing filler comprises white carbon black, and the white carbon black comprises one or a combination of three of precipitated white carbon black, gas-phase white carbon black, diatomite and quartz powder.
Preferably, the specific surface area of the reinforcing material is greater than or equal to 200m2The selection of the surface area of the fumed silica as a reinforcing material of the liquid silicone rubber influences the hardness, the apparent crosslinking degree, the initial plasticity and the modulus yield point of the silicone rubber;
specifically, the liquid silicone rubber comprises the following components in parts by mass:
Figure BDA0003109534570000131
Figure BDA0003109534570000141
the liquid silicone rubber further comprises a platinum-series catalyst, the concentration of the platinum-series catalyst is 10-40ppm, the platinum-series catalyst is a Pt-TMVDS complex in the embodiment 3 of the invention, the mass part of the Pt-TMVDS complex is 0.9 part, and the mass ratio of Si-H to vinyl in the liquid silicone rubber is 1.8; the liquid silicone rubber base rubber comprises the following components in parts by mass:
Figure BDA0003109534570000142
in example 3 of the present invention, the reinforcing filler is fumed silica cabat 2150.
Example 4:
specifically, the liquid silicone rubber comprises the following components in parts by mass:
Figure BDA0003109534570000143
the liquid silicone rubber further comprises a platinum-series catalyst, the concentration of the platinum-series catalyst is 10-40ppm, the platinum-series catalyst is a Pt-TMVDS complex in the embodiment 4 of the invention, the mass part of the Pt-TMVDS complex is 0.9 part, and the mass ratio of Si-H to vinyl in the liquid silicone rubber is 2.0; the liquid silicone rubber base rubber comprises the following components in parts by mass:
Figure BDA0003109534570000151
in example 4 of the present invention, the reinforcing filler is fumed silica deshan QS-20.
Comparative example 1 (reference example 3):
specifically, the liquid silicone rubber comprises the following components in parts by mass:
Figure BDA0003109534570000152
the liquid silicone rubber further comprises a platinum-series catalyst, the concentration of the platinum-series catalyst is 10-40ppm, the platinum-series catalyst is a Pt-TMVDS complex in the comparative example 1 of the invention, the mass part of the Pt-TMVDS complex is 0.9 part, and the mass ratio of Si-H to vinyl in the liquid silicone rubber is 2.5; the liquid silicone rubber base rubber comprises the following components in parts by mass:
Figure BDA0003109534570000153
Figure BDA0003109534570000161
in comparative example 1 of the present invention, the reinforcing filler is fumed silica CABOT 2150.
Comparative example 2 (reference example 3):
specifically, the liquid silicone rubber comprises the following components in parts by mass:
Figure BDA0003109534570000162
the liquid silicone rubber further comprises a platinum-based catalyst, the concentration of the platinum-based catalyst is 10-40ppm, the platinum-based catalyst is a Pt-TMVDS complex in comparative example 2 of the invention, the mass part of the Pt-TMVDS complex is 0.9 part, the mass ratio of Si-H to vinyl in the liquid silicone rubber is 2, and the liquid silicone rubber base rubber comprises the following components in parts by mass:
Figure BDA0003109534570000163
in comparative example 2 of the present invention, the reinforcing filler is fumed silica CABOT 2150.
Comparative example 3 (reference example 3):
specifically, the liquid silicone rubber comprises the following components in parts by mass:
Figure BDA0003109534570000171
the liquid silicone rubber further comprises a platinum-based catalyst, the concentration of the platinum-based catalyst is 10-40ppm, the platinum-based catalyst is a Pt-TMVDS complex in comparative example 3 of the invention, the mass part of the Pt-TMVDS complex is 0.9 part, the mass ratio of Si-H to vinyl in the liquid silicone rubber is 2, and the liquid silicone rubber base rubber comprises the following components in parts by mass:
Figure BDA0003109534570000172
in comparative example 3 of the present invention, the reinforcing filler is fumed silica CABOT 2150.
The group a tackifiers and group B tackifiers described in examples 3, 4 and comparative examples 1, 2, 3 above employed the structure of example 1, including the structure specifically shown and the structure not specifically shown.
The liquid silicone rubber adhesives described in examples 3, 4 and comparative examples 1, 2, 3 above were tested using the following methods:
testing the bonding strength: GBT7760-2003
It should be noted that: the liquid silicone rubbers of examples 3 and 4 and comparative examples 1, 2, and 3 described above were coated on the surface of the substrate, and were baked at 120 ℃ for 5min before being subjected to adhesion test.
And (3) testing results:
Figure BDA0003109534570000181
Figure BDA0003109534570000191
the experimental results show that cohesive failure can be realized when the liquid silicone rubbers of the embodiment 3 and the embodiment 4 are applied to a PC substrate, a PBT substrate, a PA6 substrate and an ABS substrate, compared with the embodiment 3, the comparative example 1 has the reduced components of silicone oil with vinyl groups on trimethyl-terminated side chains and a B-type tackifier, and the mass fraction of the linear silicone oil containing hydrogen on the trimethyl-terminated side chains is less than 1 part, and the obtained liquid silicone rubber has better adhesive effect when applied to the PBT substrate, can realize cohesive failure under the conditions of normal (normal temperature) and 100 ℃ water boiling for 24H, has poorer adhesive effect when applied to the PC substrate, the PA6 substrate and the ABS substrate, can be adhered under the normal (normal temperature) condition when applied to the PC substrate and the ABS substrate, but can be peeled off when 100 ℃ water boiling for 24H, and has poorer adhesive effect when applied to the PA6, adhesion cannot be achieved.
The differences between comparative example 2 and examples 3 and 4 are: comparative example 1 lacks vinyl-terminated polydimethylsiloxane and tackifier a, and it is known from the test results that the liquid silicone rubber of comparative example 2 can achieve cohesive failure when applied to a PBT substrate, and is inferior in adhesion when applied to a PC substrate, a PA6 substrate, and an ABS substrate, and from the above experimental results, it is known that the liquid silicone rubber of group a tackifier and group B tackifier are inferior in adhesion to a PC substrate, a PA6 substrate, and an ABS substrate when used alone, and that in the composition of the liquid silicone rubber proposed by the present invention including the above group a tackifier and group B tackifier, the linear silicone oil containing hydrogen in the trimethyl terminated side chain and the vinyl-terminated polydimethylsiloxane are essential components, and the respective mass ratios are respectively defined to be 1 to 5 parts and 0.01 to 20 parts.
The difference between comparative example 3 and example 3 is: the parts by mass of ethynyl cyclohexanol in comparative example 3 was 0.04 parts, whereas it was 0.06 parts in example 1. The reason why the ethynylcyclohexanol is used as a reaction inhibitor is that the liquid silicone rubber obtained is relatively poor in adhesive ability even when the ethynylcyclohexanol is used in a small amount, is limited to 0.05 to 0.5 part by mass because the liquid silicone rubber has poor flowability and adhesiveness when the ethynylcyclohexanol is used in a small amount, and the liquid silicone rubber obtained has a relatively long vulcanization time when the ethynylcyclohexanol is used in a large amount.
The preparation process of the liquid silicone rubber-based rubber comprises the following steps: the vinyl-terminated polydimethylsiloxane, the reinforcing filler, hexamethyldisilazane, tetramethyldivinylsilazane and water are put into a reactor according to the proportion, and are kneaded for 60-80 min under normal pressure and at the material temperature ranging from room temperature to 90 ℃, and are subjected to vacuum rubber mixing for 1.5-2.5H under the temperature ranging from 160 ℃ to 190 ℃ to obtain the liquid silicone rubber-based adhesive.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.

Claims (9)

1. The two-component tackifier is characterized by comprising an A-type tackifier and a B-type tackifier, wherein the A-type tackifier has the following structure:
Figure FDA0003109534560000011
wherein m + n is 30-100, m is greater than or equal to 3, and n is greater than or equal to 2;
the X is an alkyl group with a functional group, and the carbon number of the alkyl group is more than or equal to 2;
the B-type tackifier has the following structure:
Figure FDA0003109534560000012
wherein, R is1When the R3 is a hydrogen group, the R2 is an alkyl group with a functional group, when the R3 is an alkyl group with a functional group, the R2 is a hydrogen group or an alkyl group with a functional group, and the carbon number of the alkyl group in the R1, the R2 and the R3 is more than or equal to 2.
2. The two-component tackifier according to claim 1, wherein m + n is 30 to 70.
3. The two-component adhesion promoter of claim 1, wherein m is 10 to 40 and/or n is 4 to 10.
4. The two-component adhesion promoter of claim 1, wherein the functional group in X comprises one or a combination of two of phenyl, cycloalkyl.
5. A method for producing a two-component adhesion promoter for producing the two-component adhesion promoter of claims 1 to 4, comprising the steps of:
preparation of a type A tackifier:
mixing trimethyl end-capped straight-chain type hydrogen-containing silicone oil with the polymerization degree of 30-100 with an organic solvent, pouring the mixture into a first multi-neck round-bottom flask with a mechanical stirring thermometer, stirring and heating to 70-80 ℃, and stabilizing for 30 +/-10 min to obtain a straight-chain type hydrogen-containing silicone oil system, wherein the amount of the olefin monomer A with the functional group is 2-98 times that of the trimethyl end-capped straight-chain type hydrogen-containing silicone oil;
exhausting air in the first multi-mouth round-bottom flask by using inert gas;
mixing a chloroplatinic acid catalytic system and an olefin monomer A with a functional group to obtain a first drop of feed containing a catalyst, wherein the chloroplatinic acid is 5-10 ppm;
under the protection of inert gas, carrying out constant pressure titration on the straight-chain type hydrogen-containing silicone oil system by the first drop of feeding, wherein the titration time is 15-60min, after the titration is finished, continuously reacting for 1-2H at 80-100 ℃, and removing the organic solvent by rotary evaporation to obtain the A-type tackifier;
preparation of B-type tackifier:
mixing 1, 3, 5, 7-tetramethylcyclotetrasiloxane and an organic solvent, pouring the mixture into a second multi-mouth round-bottom flask with a mechanical stirring thermometer, stirring and heating to 70-80 ℃, and stabilizing for 30 +/-10 min to obtain a hydrogen-containing cyclic silicone oil system, wherein the amount of the substance of the olefin monomer B with the functional group is 2-3.9 times of that of the 1, 3, 5, 7-tetramethylcyclotetrasiloxane;
exhausting air in the second multi-mouth round-bottom flask by using inert gas;
mixing a chloroplatinic acid catalytic system and an olefin monomer B with a functional group to obtain a second drop charge containing a catalyst, wherein the chloroplatinic acid is 5-10 ppm;
under the protection of inert gas, carrying out constant pressure titration on the hydrogen-containing annular silicone oil system by using the second dropwise adding material, wherein the titration time is 15-60min, after the titration is finished, continuously reacting for 1-2H at 80-100 ℃, and removing the organic solvent by rotary evaporation to obtain the B-type tackifier.
6. A liquid silicone rubber characterized by comprising the two-component tackifier of any one of claims 1 to 4, wherein the component in parts by mass of the A-type tackifier is greater than or equal to 0.5 part, the component in parts by mass of the B-type tackifier is greater than or equal to 0.4 part, and the component in parts by mass of the B-type tackifier is as follows:
Figure FDA0003109534560000031
the silicon rubber further comprises a platinum catalyst, the concentration of the platinum catalyst is 10-40ppm, and the mass ratio of Si-H to vinyl in the liquid silicon rubber is 1.5-3.0; the liquid silicone rubber base rubber comprises the following components in parts by mass:
Figure FDA0003109534560000032
7. the liquid silicone rubber according to claim 6, wherein the part by mass of the group A tackifier is 0.5 to 3.0 parts and/or the part by mass of the group B tackifier is 0.4 to 3.0 parts.
8. The liquid silicone rubber according to claim 6, wherein the reinforcing filler comprises one or a combination of three of white carbon black, diatomaceous earth and quartz powder.
9. The method of claim 8Characterized in that the specific surface area of the reinforcing filler is greater than or equal to 200m2/g。
CN202110647165.8A 2021-06-10 2021-06-10 Two-component tackifier, liquid silicone rubber and preparation method thereof Withdrawn CN113337008A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115011305A (en) * 2022-05-25 2022-09-06 江苏斯迪克新材料科技股份有限公司 Organic silicon pressure-sensitive adhesive and preparation method thereof
CN115960358A (en) * 2022-12-23 2023-04-14 埃肯有机硅(广东)有限公司 Tackifier, secondary vulcanization-free self-adhesive addition type liquid silicone rubber and preparation method of silicone rubber

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115011305A (en) * 2022-05-25 2022-09-06 江苏斯迪克新材料科技股份有限公司 Organic silicon pressure-sensitive adhesive and preparation method thereof
CN115960358A (en) * 2022-12-23 2023-04-14 埃肯有机硅(广东)有限公司 Tackifier, secondary vulcanization-free self-adhesive addition type liquid silicone rubber and preparation method of silicone rubber
CN115960358B (en) * 2022-12-23 2024-06-11 埃肯有机硅(广东)有限公司 Tackifier, secondary vulcanization-free self-adhesive addition type liquid silicone rubber and preparation method of silicone rubber

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