CN109880585B - Liquid silicone rubber selectively bonding plastic base materials and preparation method thereof - Google Patents
Liquid silicone rubber selectively bonding plastic base materials and preparation method thereof Download PDFInfo
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Abstract
The invention provides liquid silicone rubber for selectively bonding plastic substrates, which is prepared from the following components in percentage by mass of 1: (0.8-1.2) of a component A and a component B; the component A comprises: 90 parts by weight of base material; 4-15 parts of catalyst; the component B comprises: 80-86 parts of base material; 1-10 parts of tackifier; 8-15 parts of a cross-linking agent; 0.02 to 0.1 part by weight of a crosslinking inhibitor; the base material is prepared from (1.2-1.8) by mass: 1 of vinyl silicone oil and white carbon black; the tackifier consists of organic hydrogenated polysiloxane and ester compounds containing styryl. Compared with the prior art, the liquid silicone rubber provided by the invention adopts specific content components, realizes better interaction, enables the product to be well bonded with a plastic base material under the condition of similar and compatible, and has no metal bonding property, thereby realizing good selective bonding of the plastic base material, and being suitable for application in injection molding of plastic insert products.
Description
Technical Field
The invention relates to the technical field of addition type liquid silicone rubber, in particular to liquid silicone rubber for selectively bonding plastic substrates and a preparation method thereof.
Background
The addition type liquid silicone rubber has simple injection molding process, fast molding, no toxicity and no harm, and is widely applied in the fields of automobile parts, electronic and electric appliances, infant products, tableware and the like. The addition type liquid silicone rubber has poor cohesiveness with most base materials due to the inertia of the addition type liquid silicone rubber, and in order to improve the cohesiveness with the base materials, the surface of the bonding base material is pretreated in advance by using a primer in the prior art, which often causes the problems of complicated working procedures, environmental pollution and the like; in addition, a common method is to add a tackifier into the liquid silicone rubber to improve the adhesion between the liquid silicone rubber and the base material, and compared with a method using a primer, the method has the advantages of simple process and environmental protection, and becomes a hotspot in the field of researching the adhesion of the liquid silicone rubber to the base material.
At present, although the adhesion between the addition type liquid silicone rubber and a plastic base material can be realized by adding the tackifier into the addition type liquid silicone rubber, the addition type liquid silicone rubber added with the tackifier also has good adhesion to metal and has no selectivity. The prior art discloses more compositions which have adhesiveness to addition type liquid silicone rubber, wherein the compositions comprise epoxy group and Si-H group adhesion auxiliary agents, synthesized specific organic hydrogen polysiloxane and hydrolyzable organosilicon compounds, have adhesiveness to plastics and stainless steel, and the addition of the tackifier can cause that products can not fall off from a mould well, thereby causing product defects; in another technique, hydroxy vinyl silicone oil, various silane coupling agents and bonding aids are added to bond the liquid silicone rubber and the plastic base material, but the method has high cost, more added aids and complex formula system.
Disclosure of Invention
In view of the above, the present invention provides a liquid silicone rubber selectively bonding to a plastic substrate and a method for preparing the same, wherein the liquid silicone rubber provided by the present invention can be well bonded to a plastic substrate under the condition of similar compatibility, and has no adhesion to metal.
The invention provides liquid silicone rubber for selectively bonding plastic substrates, which is prepared from the following components in percentage by mass of 1: (0.8-1.2) of a component A and a component B;
the component A comprises:
90 parts by weight of base material;
4-15 parts of catalyst;
the component B comprises:
80-86 parts of base material;
1-10 parts of tackifier;
8-15 parts of a cross-linking agent;
0.02 to 0.1 part by weight of a crosslinking inhibitor;
the base material is prepared from (1.2-1.8) by mass: 1 of vinyl silicone oil and white carbon black;
the tackifier consists of organic hydrogenated polysiloxane and ester compounds containing styryl.
Preferably, the vinyl silicone oil in the base material is α, omega-divinyl polydimethylsiloxane, and the viscosity of the α, omega-divinyl polydimethylsiloxane at 25 ℃ is 1000 mPa.s-20000 mPa.s.
Preferably, the white carbon black in the base material is hydrophobic fumed silica; the specific surface area of the white carbon black prepared by the hydrophobic gas phase method is 100m2/g～350m2/g。
Preferably, the catalyst is a platinum catalyst; the platinum content of the platinum catalyst is 2500 ppm-6000 ppm.
Preferably, the organohydrogenpolysiloxane in the adhesion promoter is selected from 1,3,5, 7-tetramethylcyclotetrasiloxane and/or a linear organohydrogenpolysiloxane.
Preferably, the styryl group-containing ester compound in the tackifier is selected from one or more of diallyl terephthalate, diallyl phthalate and diallyl isophthalate.
Preferably, the molar ratio of the Si-H of the organohydrogenpolysiloxane and Vi of the styryl group-containing ester compound in the tackifier is 1: (1-5).
Preferably, the cross-linking agent is hydrogen-containing silicone oil; the hydrogen content of the hydrogen-containing silicone oil is 0.3wt% -1.5 wt%.
Preferably, the crosslinking inhibitor is selected from methylbutynol and/or ethynylcyclohexanol.
The invention also provides a preparation method of the liquid silicone rubber, which comprises the following steps:
a) mixing vinyl silicone oil, white carbon black, hexamethyldisilazane and water, and mixing to remove hexamethyldisilazane and water to obtain a base material;
b) mixing the base material obtained in step a) with a catalyst to obtain a component A; simultaneously mixing the base material obtained in the step a) with a tackifier, a cross-linking agent and a cross-linking inhibitor to obtain a component B;
c) mixing the component A and the component B according to the mass ratio of 1: (0.8-1.2) mixing to obtain the liquid silicone rubber.
The invention provides liquid silicone rubber for selectively bonding plastic substrates, which is prepared from the following components in percentage by mass of 1: (0.8-1.2) of a component A and a component B; the component A comprises: 90 parts by weight of base material; 4-15 parts of catalyst; the component B comprises: 80-86 parts of base material; 1-10 parts of tackifier; 8-15 parts of a cross-linking agent; 0.02 to 0.1 part by weight of a crosslinking inhibitor; the base material is prepared from (1.2-1.8) by mass: 1 of vinyl silicone oil and white carbon black; the tackifier consists of organic hydrogenated polysiloxane and ester compounds containing styryl. Compared with the prior art, the liquid silicone rubber provided by the invention adopts specific content components, realizes better interaction, enables the product to be well bonded with plastic base materials (including plastics such as PC, PBT, PPSU and the like) under the condition of similarity and intermiscibility, has no bonding property to metal, namely has good demoulding property to a metal mould, realizes good selective bonding to the plastic base materials, and is suitable for being applied to injection moulding of plastic insert products.
In addition, the preparation method provided by the invention is simple and stable, does not need to additionally add a bonding auxiliary agent, is low in cost and is suitable for large-scale production and application.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides liquid silicone rubber for selectively bonding plastic substrates, which is prepared from the following components in percentage by mass of 1: (0.8-1.2) of a component A and a component B;
the component A comprises:
90 parts by weight of base material;
4-15 parts of catalyst;
the component B comprises:
80-86 parts of base material;
1-10 parts of tackifier;
8-15 parts of a cross-linking agent;
0.02 to 0.1 part by weight of a crosslinking inhibitor;
the base material is prepared from (1.2-1.8) by mass: 1 of vinyl silicone oil and white carbon black;
the tackifier consists of organic hydrogenated polysiloxane and ester compounds containing styryl.
In the invention, the liquid silicone rubber is prepared by mixing the following components in a mass ratio of 1: (0.8-1.2), preferably, the component A and the component B are prepared from the following components in a mass ratio of 1: 1, component A and component B; wherein the component A comprises:
90 parts by weight of base material;
4-15 parts of catalyst;
the component B comprises:
80-86 parts of base material;
1-10 parts of tackifier;
8-15 parts of a cross-linking agent;
0.02 to 0.1 part by weight of a crosslinking inhibitor.
In the invention, the base material is composed of vinyl silicone oil and white carbon black in a mass ratio of (1.2-1.8): 1, preferably 1.5: 1, in the invention, the vinyl silicone oil in the base material is α, omega-divinyl polydimethylsiloxane, the viscosity of the α, omega-divinyl polydimethylsiloxane at 25 ℃ is 1000 mPa.s-20000 mPa.s, more preferably 1000 mPa.s-10000 mPa.s, in a preferred embodiment of the invention, the viscosity of the α, omega-divinyl polydimethylsiloxane at 25 ℃ is 1000mPa.s, in another preferred embodiment of the invention, the viscosity of the α, omega-divinyl polydimethylsiloxane at 25 ℃ is 10000mPa.s, the invention has no special limitation on the source of the vinyl silicone oil, and the commercially available omega-divinyl polydimethylsiloxane α, which is well known by the technical personnel in the field can be adopted.
In the present invention, theThe white carbon black in the base material is preferably hydrophobic fumed silica; the specific surface area of the hydrophobic fumed silica is preferably 100m2/g～350m2A/g, more preferably 150m2/g～300m2(ii) in terms of/g. In a preferred embodiment of the invention, the specific surface area of the hydrophobic fumed silica is 150m2(ii)/g; in another preferred embodiment of the present invention, the hydrophobic fumed silica has a specific surface area of 300m2(ii) in terms of/g. The source of the white carbon black is not particularly limited in the present invention, and the white carbon black can be any commercially available or self-made product of the hydrophobic fumed silica well known to those skilled in the art.
In the present invention, the a component includes 90 parts by weight of a binder.
In the present invention, the catalyst is preferably a platinum catalyst; the platinum content of the platinum catalyst is preferably 2500ppm to 6000ppm, more preferably 5200 ppm. The source of the catalyst in the present invention is not particularly limited, and a commercially available product of the above platinum catalyst known to those skilled in the art may be used. In the present invention, the a component includes 4 to 15 parts by weight of the catalyst, preferably 10 parts by weight.
In the present invention, the base material in the component B is the same as the base material in the component A, and the description thereof is omitted. In the present invention, the B component comprises 80 to 86 parts by weight of the base material, preferably 80.94 to 85.94 parts by weight.
In the invention, the tackifier consists of organic hydrogenated polysiloxane and ester compounds containing styryl; wherein the organohydrogenpolysiloxane in the adhesion promoter is preferably selected from 1,3,5, 7-tetramethylcyclotetrasiloxane and/or linear organohydrogenpolysiloxane, more preferably 1,3,5, 7-tetramethylcyclotetrasiloxane. The source of the organohydrogenpolysiloxane is not particularly limited in the present invention, and commercially available products of the above-mentioned 1,3,5, 7-tetramethylcyclotetrasiloxane and linear organohydrogenpolysiloxane known to those skilled in the art may be used. In a preferred embodiment of the present invention, the organohydrogenpolysiloxane is a linear organohydrogenpolysiloxane, which preferably contains two or more Si — H groups in its molecule, and the hydrogen content thereof is preferably 0.1 to 2 wt%, more preferably 0.5 wt%.
In the present invention, the styryl group-containing ester compound in the tackifier is preferably selected from one or more of diallyl terephthalate, diallyl phthalate, and diallyl isophthalate, and more preferably, diallyl terephthalate. The source of the styryl group-containing ester compound is not particularly limited in the present invention, and commercially available products of the aforementioned diallyl terephthalate, diallyl phthalate and diallyl isophthalate, which are well known to those skilled in the art, may be used.
The tackifier with specific components is adopted, wherein the ester compound containing styryl contains ester group and phenyl group, the structure of the tackifier is similar to that of polycarbonate in the main molecular structure of plastic, and the tackifier and the organic hydrogenated polysiloxane are subjected to addition reaction under a catalyst to form a compound with a structure similar to that of a plastic base material, so that the compound and the plastic base material are well bonded under the condition of similar compatibility.
In the present invention, the molar ratio of Si — H of the organohydrogenpolysiloxane and Vi of the styryl group-containing ester compound in the tackifier is preferably 1: (1-5), more preferably 1: (1-1.5). According to the invention, the molar ratio of Si-H of the organic hydrogenated polysiloxane to Vi of the styryl-containing ester compound is regulated, so that the obtained liquid silicone rubber and the plastic base material are well bonded, and the bonding of the silicone rubber to a metal mold is not generated in the process, so that the silicone rubber has good selective bonding to the plastic base material, and the silicone rubber is very suitable for injection molding of plastic insert products.
In the present invention, the B component includes 1 to 10 parts by weight of a tackifier, preferably 4 to 6 parts by weight.
In the present invention, the crosslinking agent is preferably a hydrogen-containing silicone oil; the hydrogen content of the hydrogen-containing silicone oil is preferably 0.3wt% to 1.5wt%, and more preferably 0.5 wt%. The source of the crosslinking agent in the present invention is not particularly limited, and commercially available products of the above hydrogen-containing silicone oil known to those skilled in the art can be used. In the present invention, the B component includes 8 to 15 parts by weight of a crosslinking agent, preferably 10 to 13 parts by weight.
In the present invention, the crosslinking inhibitor is preferably selected from methylbutynol and/or ethynylcyclohexanol, more preferably ethynylcyclohexanol. The source of the crosslinking inhibitor in the present invention is not particularly limited, and commercially available products of the above-mentioned methylbutynol and ethynylcyclohexanol, which are well known to those skilled in the art, may be used. In the present invention, the B component includes 0.02 to 0.1 parts by weight of a crosslinking inhibitor, preferably 0.06 parts by weight.
The liquid silicone rubber provided by the invention adopts specific content components, realizes better interaction, enables the product to be well bonded with plastic base materials (including plastics such as PC, PBT, PPSU and the like) under the condition of similar and compatible, and has no bonding property to metal, namely, good demoulding property to metal moulds, thereby realizing good selective bonding to the plastic base materials; and the mechanical strength of the vulcanized product is high, so that the vulcanized product is very suitable for being applied to injection molding of plastic insert products.
The invention also provides a preparation method of the liquid silicone rubber, which comprises the following steps:
a) mixing vinyl silicone oil, white carbon black, hexamethyldisilazane and water, and mixing to remove hexamethyldisilazane and water to obtain a base material;
b) mixing the base material obtained in step a) with a catalyst to obtain a component A; simultaneously mixing the base material obtained in the step a) with a tackifier, a cross-linking agent and a cross-linking inhibitor to obtain a component B;
c) mixing the component A and the component B according to the mass ratio of 1: (0.8-1.2) mixing to obtain the liquid silicone rubber.
Firstly, mixing vinyl silicone oil, white carbon black, hexamethyldisilazane and water, and carrying out mixing to remove the hexamethyldisilazane and the water to obtain a base material. In the present invention, the vinyl silicone oil and the white carbon black are the same as those described in the above technical scheme, and are not described herein again.
In the invention, the mass ratio of the vinyl silicone oil, the white carbon black, the hexamethyldisilazane and the water is preferably (1.2-1.8): 1: (0.2-0.3): (0.04 to 0.06), more preferably 1.5: 1: 0.25: 0.05.
the equipment for the mixing and subsequent mixing process is not particularly limited in the present invention, and a kneader well known to those skilled in the art may be used. In the present invention, the mixing process preferably includes:
mixing the mixed materials for 2 to 3 hours at the temperature of between 20 and 30 ℃, then heating to the temperature of between 95 and 105 ℃, mixing for 0.4 to 0.6 hour, heating to the temperature of between 135 and 15 ℃, and mixing in vacuum for 2 to 4 hours to obtain a base material;
more preferably:
mixing the mixed materials at 25 ℃ for 2.5h, heating to 100 ℃ for 0.5h, and then heating to 140-150 ℃ for 3h in vacuum to obtain the base material. In the present invention, the degree of vacuum in the vacuum kneading is preferably 0.08MPa to 0.1 MPa. The purpose of the mixing process adopted by the invention is to uniformly mix the vinyl silicone oil and the white carbon black and simultaneously remove hexamethyldisilazane and water.
After the base material is obtained, mixing the obtained base material with a catalyst to obtain a component A; and simultaneously mixing the obtained base material with a tackifier, a crosslinking agent and a crosslinking inhibitor to obtain a component B. The invention has no special limitation on the specific process of mixing the base material and the catalyst and the specific process of mixing the base material, the tackifier, the crosslinking agent and the crosslinking inhibitor, and can adopt the technical scheme of mechanical stirring or manual stirring which is well known by the technical personnel in the field, so that the components in the component A and the components in the component B are uniformly mixed respectively.
After the component A and the component B are obtained, the component A and the component B are mixed according to the mass ratio of 1: (0.8-1.2) mixing to obtain liquid silicone rubber; preferably, the component A and the component B are mixed according to the mass ratio of 1: 1, mixing to obtain the liquid silicone rubber. The specific process of mixing the component A and the component B is not particularly limited in the invention, and the technical scheme of mechanical stirring or manual stirring which is well known to those skilled in the art can be adopted, so that the component A and the component B are uniformly mixed.
The preparation method provided by the invention has the advantages of simple process and formula, stable production, no need of additional bonding auxiliary agent, low cost, few added components, easiness in repetition and suitability for large-scale production and application.
The invention provides liquid silicone rubber for selectively bonding plastic substrates, which is prepared from the following components in percentage by mass of 1: (0.8-1.2) of a component A and a component B; the component A comprises: 90 parts by weight of base material; 4-15 parts of catalyst; the component B comprises: 80-86 parts of base material; 1-10 parts of tackifier; 8-15 parts of a cross-linking agent; 0.02 to 0.1 part by weight of a crosslinking inhibitor; the base material is prepared from (1.2-1.8) by mass: 1 of vinyl silicone oil and white carbon black; the tackifier consists of organic hydrogenated polysiloxane and ester compounds containing styryl. Compared with the prior art, the liquid silicone rubber provided by the invention adopts specific content components, realizes better interaction, enables the product to be well bonded with plastic base materials (including plastics such as PC, PBT, PPSU and the like) under the condition of similarity and intermiscibility, has no bonding property to metal, namely has good demoulding property to a metal mould, realizes good selective bonding to the plastic base materials, and is suitable for being applied to injection moulding of plastic insert products.
In addition, the preparation method provided by the invention is simple and stable, does not need to additionally add a bonding auxiliary agent, is low in cost and is suitable for large-scale production and application.
In order to further illustrate the present invention, the following examples are given in detail, wherein the raw materials used in the following examples are commercially available, wherein the phenyl-containing vinyl ester compounds (including diallyl terephthalate, diallyl phthalate and diallyl isophthalate) are obtained from Tokyo technologies, Inc., the vinyl silicone oil (including α, omega-divinylpolydimethylsiloxane having a viscosity of 1000mPa.s and α, omega-divinylpolydimethylsiloxane having a viscosity of 10000 mPa.s), the hydrogen-containing silicone oil and the hydrophobic gas phase process are provided by Xinjiang Anchen chemical corporation, Inc., and the catalyst is platinum catalyst having a platinum content of 5200 ppm.
Example 1
(1) Preparing a base material: will be provided with60 parts by weight of α, omega-divinylpolydimethylsiloxane having a viscosity (25 ℃) of 1000 mPas, 40 parts by weight of a specific surface area of 150m2Putting the hydrophobic fumed silica, 10 parts by weight of hexamethyldisilazane and 2 parts by weight of water into a kneader, mixing for 2.5h at 25 ℃, then heating to 100 ℃, mixing for 0.5h, heating to 140-150 ℃, and mixing for 3h under vacuum (the vacuum degree is 0.08-0.1 MPa) to obtain the base material.
(2) Preparation of component A: and (2) taking 90g of the base material obtained in the step (1), adding 10g of catalyst, and stirring for 10-30 min to obtain the component A.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl terephthalate, the molar ratio of Si-H to Si-Vi between the two is 1: 1), 13g of hydrogen-containing silicone oil (with the hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain the component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 2
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl terephthalate, the molar ratio of Si-H to Si-Vi between the two is 1: 1.2), 13g of hydrogen-containing silicone oil (with the hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain the component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 3
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl terephthalate, the molar ratio of Si-H to Si-Vi between the two is 1: 1.3), 13g of hydrogen-containing silicone oil (with the hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain the component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 4
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl terephthalate, the molar ratio of Si-H to Si-Vi between the two is 1: 1.4), 13g of hydrogen-containing silicone oil (with the hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain the component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 5
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl terephthalate, the molar ratio of Si-H to Si-Vi between the two is 1: 1.5), 13g of hydrogen-containing silicone oil (with the hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain the component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 6
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl phthalate, wherein the molar ratio of Si-H to Si-Vi between the two is 1: 1.3), 13g of hydrogen-containing silicone oil (with the hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain the component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 7
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl isophthalate, the molar ratio of Si-H: Si-Vi between the two is 1: 1.3), 13g of hydrogen-containing silicone oil (the hydrogen content is 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain a component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 8
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of linear organic hydrogenated polysiloxane (with hydrogen content of 0.1%) and diallyl terephthalate, the molar ratio of Si-H: Si-Vi between the two is 1: 1.3), 13g of hydrogen-containing silicone oil (with hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain a component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 9
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of linear organic hydrogenated polysiloxane (with hydrogen content of 0.3%) and diallyl terephthalate with the molar ratio of Si-H: Si-Vi of 1: 1.3), 13g of hydrogen-containing silicone oil (with hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain a component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 10
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of linear organic hydrogenated polysiloxane (with hydrogen content of 0.5%) and diallyl terephthalate with the molar ratio of Si-H: Si-Vi of 1: 1.3), 13g of hydrogen-containing silicone oil (with hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain a component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 11
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of linear organic hydrogenated polysiloxane (with hydrogen content of 0.8%) and diallyl terephthalate with the molar ratio of Si-H: Si-Vi of 1: 1.3), 13g of hydrogen-containing silicone oil (with hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain a component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 12
(1) Preparing a base material: the same as in example 1.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of linear organic hydrogenated polysiloxane (hydrogen content is 1.6%) and diallyl terephthalate, the molar ratio of Si-H: Si-Vi between the two is 1: 1.3), 13g of hydrogen-containing silicone oil (hydrogen content is 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain a component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 13
(1) The base was prepared by mixing 60 parts by weight of α, omega-divinylpolydimethylsiloxane having a viscosity (25 ℃ C.) of 10000mPa.s, 40 parts by weight of a specific surface area of 300m2Putting the hydrophobic fumed silica, 10 parts by weight of hexamethyldisilazane and 2 parts by weight of water into a kneader, mixing for 2.5h at 25 ℃, then heating to 100 ℃, mixing for 0.5h, heating to 140-150 ℃, and mixing for 3h under vacuum (the vacuum degree is 0.08-0.1 MPa) to obtain the base material.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: 80.94g of the base material obtained in the step (1) is taken, 6g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl terephthalate, the molar ratio of Si-H to Si-Vi between the two is 1: 1.3), 13g of hydrogen-containing silicone oil (with the hydrogen content of 0.5%) and 0.06g of ethynyl cyclohexanol are added, and the mixture is stirred for 10-30 min to obtain the component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
Example 14
(1) Preparing a base material: the same as in example 13.
(2) Preparation of component A: the same as in example 1.
(3) Preparation of the component B: taking 85.94g of the base material obtained in the step (1), adding 4g of tackifier (consisting of 1,3,5, 7-tetramethylcyclotetrasiloxane and diallyl terephthalate, wherein the molar ratio of Si-H: Si-Vi between the two is 1: 1.3), 10g of hydrogen-containing silicone oil (the hydrogen content is 0.5%) and 0.06g of ethynyl cyclohexanol, and stirring for 10-30 min to obtain the component B.
(4) Preparation of liquid silicone rubber for selective bonding to plastic substrates: mixing the component A obtained in the step (2) and the component B obtained in the step (3) according to the weight ratio of 1: 1, and uniformly mixing to obtain the product.
The liquid silicone rubber prepared in the embodiments 1-14 of the invention is tested for various properties, and the results are shown in tables 1-2.
TABLE 1 data of various properties of liquid silicone rubbers prepared in inventive examples 1-7
TABLE 2 data of various properties of liquid silicone rubbers prepared in inventive examples 8-14
As can be seen from tables 1-2: (1) as can be seen from comparison of examples 1 to 5, the change in the molar ratio of Si-H in 1,3,5, 7-tetramethylcyclotetrasiloxane and Si-Vi in diallyl terephthalate in the tackifier affects the degree of cohesive failure between the liquid silicone rubber and the substrate when the ratio of Si-H: the molar ratio of Si-Vi is 1: 1.3, the cohesiveness of the liquid silicone rubber and various plastic base materials reaches the best, the cohesive failure degree of the liquid silicone rubber to PC and PET reaches 100 percent, and the cohesive failure degree of the liquid silicone rubber to PPSU reaches 80 percent; when the ratio of Si-H: as the Si-Vi molar ratio continues to decrease, the degree of cohesive failure of the liquid silicone rubber and various plastic substrates decreases, and the mechanical properties, other than hardness, decrease.
(2) As can be seen from the comparison of examples 3, 6 and 7, the styrene-containing ester compound in the tackifier is diallyl terephthalate, so that the obtained liquid silicone rubber can achieve the best bonding effect with various plastic substrates.
(3) It can be seen from comparison of examples 8 to 12 that when the hydrogen content of the linear organohydrogenpolysiloxane in the tackifier reaches 1.6%, a certain amount of cohesive failure occurs between the liquid silicone rubber and various plastic substrates.
(4) The liquid silicone rubber selectively bonded to the plastic base material prepared in examples 1 to 14 is excellent in tensile strength, elongation at break and tear strength after vulcanization, and has no adhesion to metal; among them, the most preferable results in example 3 are the best adhesion to various plastic substrates.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A liquid silicone rubber for selectively bonding plastic substrates is prepared from the following components in a mass ratio of 1: (0.8-1.2) of a component A and a component B;
the component A comprises:
90 parts by weight of base material;
4-15 parts by weight of a catalyst;
the component B comprises:
80-86 parts by weight of a base material;
1-10 parts by weight of a tackifier;
8-15 parts by weight of a crosslinking agent;
0.02 to 0.1 parts by weight of a crosslinking inhibitor;
the base material is prepared from (1.2-1.8) by mass: 1 of vinyl silicone oil and white carbon black;
the tackifier consists of organic hydrogenated polysiloxane and ester compounds containing styryl; the organohydrogenpolysiloxane in the tackifier is selected from 1,3,5, 7-tetramethylcyclotetrasiloxane and/or linear organohydrogenpolysiloxane; the linear organohydrogenpolysiloxane had a hydrogen content of 1.6 wt%.
2. The liquid silicone rubber according to claim 1, wherein the vinyl silicone oil in the base is α, omega-divinyl polydimethylsiloxane, and the viscosity of the α, omega-divinyl polydimethylsiloxane at 25 ℃ is 1000mPa.s to 20000 mPa.s.
3. The liquid silicone rubber according to claim 1, wherein the white carbon black in the base material is hydrophobic fumed silica; the specific surface area of the white carbon black prepared by the hydrophobic gas phase method is 100m2/g~350m2/g。
4. The liquid silicone rubber according to claim 1, wherein the catalyst is a platinum catalyst; the platinum content of the platinum catalyst is 2500 ppm-6000 ppm.
5. The liquid silicone rubber according to claim 1, wherein the styryl group-containing ester compound in the tackifier is selected from one or more of diallyl terephthalate, diallyl phthalate, and diallyl isophthalate.
6. The liquid silicone rubber according to claim 1, wherein the molar ratio of Si-H of the organohydrogenpolysiloxane to Vi of the styryl group-containing ester compound in the tackifier is 1: (1-5).
7. The liquid silicone rubber according to claim 1, wherein the crosslinking agent is a hydrogen-containing silicone oil; the hydrogen content of the hydrogen-containing silicone oil is 0.3wt% -1.5 wt%.
8. The liquid silicone rubber according to claim 1, wherein the crosslinking inhibitor is selected from methylbutynol and/or ethynylcyclohexanol.
9. A method for preparing the liquid silicone rubber according to any one of claims 1 to 8, comprising the steps of:
a) mixing vinyl silicone oil, white carbon black, hexamethyldisilazane and water, and mixing to remove hexamethyldisilazane and water to obtain a base material;
b) mixing the base material obtained in step a) with a catalyst to obtain a component A; simultaneously mixing the base material obtained in the step a) with a tackifier, a cross-linking agent and a cross-linking inhibitor to obtain a component B;
c) mixing the component A and the component B according to the mass ratio of 1: (0.8-1.2) mixing to obtain the liquid silicone rubber.
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| CN111909380A (en) * | 2020-07-17 | 2020-11-10 | 浙江新安化工集团股份有限公司 | Addition type liquid silicone rubber tackifier, and preparation method and application thereof |
| CN112111222A (en) * | 2020-09-10 | 2020-12-22 | 江苏天辰新材料股份有限公司 | Double-component addition type silicone rubber for priming-free polyamide base material and preparation method thereof |
| CN113004704B (en) * | 2021-04-01 | 2023-11-21 | 湖北航泰科技有限公司 | Silicon rubber, preparation method thereof and silicon rubber elastic piece |
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