CN111072970A - Room-temperature tackifier and preparation method and application thereof - Google Patents

Room-temperature tackifier and preparation method and application thereof Download PDF

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CN111072970A
CN111072970A CN201911419872.0A CN201911419872A CN111072970A CN 111072970 A CN111072970 A CN 111072970A CN 201911419872 A CN201911419872 A CN 201911419872A CN 111072970 A CN111072970 A CN 111072970A
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tackifier
room temperature
room
temperature
octamethylcyclotetrasiloxane
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刘金明
胡国新
林旭锋
陈柏富
陈双涌
李江华
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Zhaoshun Technology (guangdong) Co Ltd
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Zhaoshun Technology (guangdong) Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention provides a room-temperature tackifier and a preparation method and application thereof. The room-temperature tackifier has a structure shown as a formula I, wherein m and n are respectively and independently selected from integers more than 0; r1Selected from C1-C10 alkylene, R2、R3、R4、R5、R6And R7The same or different, each independently selectedAny one of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl or C6-C30 aryl, and R4、R5、R6Or R7At least one of which is selected from C2-C10 alkenyl. The tackifier provided by the invention has good compatibility with addition type silicone rubber, can bond the addition type silicone rubber and a bonded surface at room temperature, obviously improves the bonding property of the addition type silicone rubber, and has the advantages of simple preparation method and mild reaction conditions.

Description

Room-temperature tackifier and preparation method and application thereof
Technical Field
The invention relates to the technical field of addition type silicone rubber, in particular to a tackifier and a preparation method and application thereof, and especially relates to a room-temperature tackifier and a preparation method and application thereof.
Background
The addition type silicone rubber is vulcanized and formed by hydrosilylation of polysiloxane containing vinyl and polysiloxane containing a polysiloxane hydrogen bond under the action of a platinum catalyst. The addition type silicon rubber does not generate byproducts in the vulcanization process, and has the excellent performances of relatively low vulcanization temperature, short vulcanization time and the like, so that the addition type silicon rubber can be widely applied. However, the addition type silicone rubber has the defects of weak acting force with the adhered surface and poor adhesive property, so that the addition type silicone rubber needs to be treated by using a primer or a tackifier, and the adhesive property of the addition type silicone rubber to a substrate is improved.
However, the use of a primer increases the number of processes, which leads to an increase in use cost and workload, and uses an organic solvent, which is environmentally undesirable due to the large amount of organic solvent used; the use of the tackifier generally has the problems of little improvement on the bonding performance, and the problems of viscosity increase, turbidity and the like of addition type silicone rubber. The proper tackifier is required to have good compatibility with the main components of the addition type silicone rubber, and does not influence the curing process of the silicone rubber and various physical and mechanical properties and electrical properties after curing.
CN105001422A discloses a tackifier for addition type silicone rubber, a preparation method thereof and addition type silicone rubber, wherein the preparation method comprises the following steps: adding phenyl silicone oil with high hydrogen content and toluene into a reactor, heating, and adding a platinum catalyst; after being mixed evenly, KH570 is added for reaction; adding allyl glycidyl ether to react for 1 hour at the temperature of 60-100 ℃, and removing low-boiling-point substances to obtain the tackifier. The tackifier for the addition type silicone rubber prepared by the method is colorless and transparent liquid, has no peculiar smell, has good stability and can be stored for a long time. The obtained addition type silicone rubber is used as a tackifier, and can improve the adhesion of the addition type silicone rubber with a base material after being cured at medium temperature. However, the silicone rubber prepared by the tackifier provided by the invention needs to be cured at a medium temperature, and extra steps and instruments and equipment are needed during use, so that the use is inconvenient.
CN104497906A discloses a boron-containing tackifier for addition type silicone rubber and a preparation method thereof. The preparation method comprises the following steps: (1) mixing borohydride, unsaturated bond-containing silane and solvent; the unsaturated bond-containing silane is a vinyl group-containing silane; the solvent is an ether solvent; (2) and (2) dropwise adding a boron trifluoride complex compound into the mixture obtained in the step (1), and reacting to obtain the boron-containing tackifier. The preparation method is novel, simple and efficient, the product purity is high, the operation process is simple, and the method is suitable for industrial production, so that the application range of the addition type silicone rubber as an adhesive and a sealant is greatly expanded, meanwhile, the boron-containing tackifier has a wide application range, and the bonding performance of the addition type silicone rubber to substrates such as stainless steel, aluminum, brass, PET or PC can be improved. Although the boron-containing tackifier has a wide application range, the silicon rubber prepared by using the boron-containing tackifier still needs high-temperature curing to be combined with a substrate.
At present, the preparation method of the tackifier mainly comprises synthesis, and various organic groups are introduced into the structure of the tackifier. The tackifier can increase the adhesion between the addition type silicone rubber and the base material to a certain extent, but has the defects of complex preparation method, incapability of improving the adhesion capability of the silicone rubber, capability of using the prepared silicone rubber after high-temperature curing and the like.
Therefore, it is urgent to find a suitable tackifier to improve the adhesive strength of the addition type silicone rubber and to simplify the use conditions of the addition type silicone rubber.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the room-temperature tackifier which has better compatibility with addition type silicone rubber, can improve the bonding strength of the addition type silicone rubber, and can realize the bonding of the silicone rubber and a bonded surface at room temperature. In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a room temperature tackifier having a structure represented by formula I:
Figure BDA0002352061420000031
wherein m and n are each independently selected from integers greater than 0; r1C1-C10 alkylene, for example, C1, C2, C3, C5, C6, C7, C8 or C9 alkylene; r2、R3、R4、R5、R6And R7The same or different, each is independently selected from any one of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl or C6-C30 aryl, wherein C1-C10 alkyl can be C1, C5, C6, C7, C8 or C9 alkyl, C2-C10 alkenyl can be C2, C3, C5, C6, C7, C8 or C9 alkenyl, C2-C10 alkynyl can be C3, C5, C6, C7, C8 or C9 alkynyl, C6-C30 aryl can be C6, C7, C8, C10, C12, C15, C20, C22, C25 or C30 aryl, and R is R30 aryl4、R5、R6Or R7At least one of which is selected from C2-C10 alkenyl.
The room temperature tackifier provided by the invention can obviously improve the adhesion of addition type silicone rubber, and can realize the adhesion of the silicone rubber and the adhered surface at room temperature.
As a preferred technical scheme of the invention, the structural formula of the room-temperature tackifier is as follows:
Figure BDA0002352061420000032
wherein m and n are each independently selected from integers greater than 0.
Preferably, m is selected from an integer from 1 to 100, and may be, for example, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100, etc., preferably 10 to 50.
Preferably, n is selected from integers from 1 to 20, and may be, for example, 1, 2, 5, 6, 8, 10, 12, 14, 16, 18 or 20, etc., preferably from 1 to 5.
In the invention, R of the room-temperature tackifier1is-CH2CH2CH2-，R2、R3、R4、R5And R6Are each methyl, R7Is composed of
Figure BDA0002352061420000041
The tackifier is added into addition type silicone rubber, the adhesion of the silicone rubber can be obviously improved, meanwhile, the silicone rubber does not need to be subjected to high temperature during curing and forming, and the room-temperature tackifier can be bonded with a bonded surface at room temperature.
In a preferred embodiment of the present invention, the viscosity of the room temperature tackifier is 5 to 800cps, and may be, for example, 5cps, 20cps, 50cps, 80cps, 100cps, 150cps, 200cps, 250cps, 280cps, 300cps, 350cps, 400cps, 450cps, 500cps, 550cps, 600cps, 650cps, 700cps, 750cps, 800cps, or the like.
Preferably, the weight average molecular weight of the room temperature tackifier is 888-500000, which may be 900, 1000, 1100, 1200, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 8000, 10000, 15000, 20000, 50000, 80000, 100000, 200000, 300000, 400000 or 500000, etc., preferably 1000-5000.
In a second aspect, the present invention provides a method for preparing the room temperature tackifier as described in the first aspect, the method comprising the steps of:
will be provided with
Figure BDA0002352061420000042
And (3) carrying out reaction to prepare the room-temperature tackifier.
Preferably, the
Figure BDA0002352061420000043
Is octamethylcyclotetrasiloxane.
Preferably, the
Figure BDA0002352061420000051
Is tetramethyl tetravinylcyclotetrasiloxane.
Preferably, the
Figure BDA0002352061420000052
Is 1, 3-bis (3-aminopropyl) tetramethyldisiloxane.
In the invention, octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane can be used as basic polymers, and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is used for end capping to obtain the required tackifier. The preparation method has the advantages of simple reaction conditions, mild reaction conditions and high efficiency, and is suitable for preparation of the tackifier.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) to pair
Figure BDA0002352061420000053
Dehydrating;
(2) after dehydration
Figure BDA0002352061420000054
And the above-mentioned
Figure BDA0002352061420000055
And reacting under the action of a catalyst to obtain the room-temperature tackifier.
Preferably, the
Figure BDA0002352061420000061
The molar ratio of (1-1000):1, for example, may be 1:1, 10:1, 50:1, 100:1, 200:1, 300:1, 350:1, 400:1, 450:1, 500:1, 550:1, 600:1, 700:1, 800:1, 900:1 or 1000:1, preferably (1-50):1, more preferably (5-20): 1. When the molar ratio of the two is within the preferred range, the reaction efficiency is high and the adhesive properties of the resulting product are good.
Preferably, the
Figure BDA0002352061420000062
And
Figure BDA0002352061420000063
the molar ratio of (1-10000):1, for example, may be 1:1, 10:1, 100:1, 200:1, 500:1, 600:1, 800:1, 1000:1, 1200:1, 1300:1, 1400:1, 1500:1, 1600:1, 1800:1, 2000:1, 3000:1, 4000:1, 5000:1, 6000:1, 7000:1, 8000:1, 9000:1 or 10000:1, and preferably (10-100): 1. When the molar ratio of the two is in the preferable range, the amino-terminated rate of the obtained product is higher, and the bonding effect of the obtained adhesive is better.
In a preferred embodiment of the present invention, the catalyst is selected from potassium hydroxide, tetramethylammonium hydroxide, and ammonia water.
Preferably, the mass concentration of the ammonia water is 2 to 50%, and may be, for example, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or the like.
Preferably, the catalyst is used in an amount of
Figure BDA0002352061420000071
0.0005 to 0.05 wt% of the total weight, for example, may be 0.0005 wt%, 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.025 wt%, 0.028 wt%, 0.03 wt%, 0.032 wt%, 0.035 wt%, 0.04 wt%, 0.045 wt%, 0.05 wt%, or the like.
Preferably, said step (1)
Figure BDA0002352061420000072
The dehydration time is 30-120min, such as 30min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, and the temperature is 50-80 deg.C, such as 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 72 deg.C, 75 deg.C or 80 deg.C.
In the present invention, step (1) may be performed on
Figure BDA0002352061420000073
The dehydration may be performed separately or by mixing them.
Preferably, the reaction temperature in step (2) is 80-120 deg.C, such as 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C or 120 deg.C, and the reaction time is 1-6h, such as 1h, 1.2h, 1.5h, 2h, 2.2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6 h.
Preferably, step (2) further comprises removing low-boiling substances after the reaction is finished.
Preferably, the temperature for removing the low boiling substance is 120-.
As a preferred technical scheme of the invention, octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane are used as raw materials to prepare the room-temperature tackifier, and the preparation method comprises the following steps:
(1) dehydrating octamethylcyclotetrasiloxane at 50-80 deg.C for 30-120min, and dehydrating tetramethyltetravinylcyclotetrasiloxane at 50-80 deg.C for 30-120 min;
(2) mixing the dehydrated octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane with 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, reacting for 1-6h at 80-120 ℃ under the action of a catalyst, then heating to 120-180 ℃ and maintaining for 1-6h to remove low-boiling-point substances, thereby obtaining the room-temperature tackifier.
In a third aspect, the invention also provides a use of the room temperature tackifier as described in the first aspect in the preparation of an addition type silicone rubber.
Compared with the prior art, the invention has the following beneficial effects:
the room temperature tackifier provided by the invention has good compatibility with addition type silicone rubber, can obviously improve the bonding property of the addition type silicone rubber, can enable the bonding effect of the silicone rubber and a bonded surface to be better when used at room temperature, and meanwhile, the preparation method provided by the invention has the advantages of simple operation, mild reaction conditions, high efficiency and easiness in preparation of the room temperature tackifier.
Drawings
FIG. 1 is an infrared spectrum of the room temperature tackifier prepared in example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
This example provides a room temperature tackifier that may be represented using the following structural formula:
Figure BDA0002352061420000091
wherein m is 10 and n is 1. The room temperature tackifier is detected by using an FTIR920 Fourier transform infrared spectrometer, and the obtained infrared spectrogram is shown in figure 1, 779cm-1Stretching vibration and CH of Si-C3In-plane rocking of 1020cm-1And 1093cm-1Belongs to the stretching vibration absorption peak of Si-O-Si, 1260cm-1And 1409cm-1Is Si-CH3In (C-CH)31650cm, caused by in-plane and out-of-plane bending vibrations-1The weak peak is-CH ═ CH2Vibration of 3400cm-1And 3500cm-1The position is two symmetric stretching vibration peaks of H on primary amine.
The preparation method comprises the following steps:
(1) 1mol of octamethylcyclotetrasiloxane (Tangshan Sanyou silicon, Inc.) and 0.1mol of tetramethyltetravinylcyclotetrasiloxane (Zhejiang orange organosilicon, Inc.) were dehydrated at 60 deg.C for 60min, respectively;
(2) mixing the dehydrated octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane with 0.4mol of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (Hubei Xin Rundy chemical Co., Ltd.), reacting for 4h at 100 ℃ under the action of 1.5g of potassium hydroxide, then heating to 150 ℃ and maintaining for 4h to remove low-boiling-point substances, thus obtaining the room-temperature tackifier, wherein the weight-average molecular weight of the tackifier is 1074, and the viscosity of the tackifier is 30 cps.
Example 2
This example provides a room temperature tackifier that may be represented using the following structural formula:
Figure BDA0002352061420000101
wherein m is 20 and n is 1.
The preparation method comprises the following steps:
(1) 2mol of octamethylcyclotetrasiloxane and 0.1mol of tetramethyltetravinylcyclotetrasiloxane are dehydrated for 30min at 80 ℃;
(2) mixing the dehydrated octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane with 0.4mol of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, reacting at 80 ℃ for 6h under the action of 1g of potassium hydroxide, then heating to 180 ℃ and maintaining for 2h to remove low-boiling-point substances, thus obtaining the room-temperature tackifier, wherein the weight-average molecular weight of the tackifier is 1814, and the viscosity of the tackifier is 35 cps.
Example 3
This example provides a room temperature tackifier that may be represented using the following structural formula:
Figure BDA0002352061420000102
wherein m is 10 and n is 2.
The preparation method comprises the following steps:
(1) dehydrating 1mol of octamethylcyclotetrasiloxane and 0.2mol of tetramethyltetravinylcyclotetrasiloxane at 80 ℃ for 120min respectively;
(2) mixing the dehydrated octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane with 0.4mol of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, reacting at 120 ℃ for 1h under the action of 0.05g of potassium hydroxide, heating to 120 ℃ and maintaining for 6h to remove low-boiling-point substances, thus obtaining the room-temperature tackifier, wherein the weight-average molecular weight of the tackifier is 1160, and the viscosity of the tackifier is 28 cps.
Example 4
This example provides a room temperature tackifier that may be represented using the following structural formula:
Figure BDA0002352061420000111
wherein m is 50 and n is 1.
The preparation method comprises the following steps:
(1) 5mol of octamethylcyclotetrasiloxane and 0.1mol of tetramethyltetravinylcyclotetrasiloxane are dehydrated for 100min at 60 ℃ respectively;
(2) mixing the dehydrated octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane with 0.4mol of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, reacting for 6h at 100 ℃ under the action of 1g of potassium hydroxide, then heating to 120 ℃ and maintaining for 6h to remove low-boiling-point substances, thus obtaining the room-temperature tackifier, wherein the weight-average molecular weight of the tackifier is 4034, and the viscosity of the tackifier is 65 cps.
Comparative example 1
This comparative example provides a tackifier that may be represented using the following structural formula:
Figure BDA0002352061420000112
wherein m is 10 and n is 1.
The preparation method of the tackifier comprises the following steps:
(1) 1mol of octamethylcyclotetrasiloxane and 0.1mol of tetramethyltetravinylcyclotetrasiloxane are dehydrated for 60min at 60 ℃ respectively;
(2) reacting the dehydrated octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane at 100 ℃ for 4 hours under the action of 1.5g of potassium hydroxide, then heating to 150 ℃ and maintaining for 4 hours to remove low-boiling-point substances, thus obtaining the room-temperature tackifier, wherein the weight-average molecular weight of the tackifier is 988, and the viscosity of the tackifier is 25 cps.
Comparative example 2
This comparative example provides a tackifier that may be represented using the following structural formula:
Figure BDA0002352061420000121
wherein m is 20.
The preparation method of the tackifier comprises the following steps:
(1) dehydrating 2mol of octamethylcyclotetrasiloxane at 60 ℃ for 60 min;
(2) mixing the dehydrated octamethylcyclotetrasiloxane and 0.4mol of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, reacting for 4 hours at 100 ℃ under the action of 1.5g of potassium hydroxide, then heating to 150 ℃ and maintaining for 4 hours to remove low-boiling-point substances, thus obtaining the room-temperature tackifier, wherein the weight-average molecular weight of the tackifier is 1728, and the viscosity of the tackifier is 33 cps.
Comparative example 3
This comparative example provides a tackifier that may be represented using the following structural formula:
Figure BDA0002352061420000122
wherein n is 2.
The preparation method of the tackifier comprises the following steps:
(1) dehydrating 0.2mol of tetramethyltetravinylcyclotetrasiloxane at 60 ℃ for 60 min;
(2) mixing the dehydrated tetramethyltetravinylcyclotetrasiloxane and 0.4mol of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, reacting for 4 hours at 100 ℃ under the action of 1.5g of potassium hydroxide, then heating to 150 ℃ and maintaining for 4 hours to remove low-boiling-point substances, thus obtaining the room-temperature tackifier, wherein the weight-average molecular weight of the tackifier is 420, and the viscosity of the tackifier is 18 cps.
Comparative example 4
This comparative example provides a tackifier, which is different from example 1 in that the amount of tetramethyltetravinylcyclotetrasiloxane used is 2mol, the remaining conditions are the same as example 1, and the weight average molecular weight of the tackifier obtained is 1814 and the viscosity is 35 cps.
Comparative example 5
This comparative example provides a tackifier, which is different from example 1 in that tetramethyltetravinylcyclotetrasiloxane is used in an amount of 1mol, and the remaining conditions are the same as example 1, and the weight average molecular weight of the tackifier is 1748 and the viscosity is 30 cps.
Comparative example 6
This comparative example provides a tackifier, which is different from example 1 in that 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is used in an amount of 0.8mol, and the remaining conditions are the same as example 1, and the tackifier has a weight average molecular weight of 568 and a viscosity of 20 cps.
Comparative example 7
This comparative example provides a tackifier, which is different from example 1 in that 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is used in an amount of 0.04mol, and the remaining conditions are the same as example 1, and the tackifier has a weight average molecular weight of 8508 and a viscosity of 140 cps.
Performance testing
Adhesion Performance test
5 parts by weight of the tackifiers provided in examples 1 to 4 and comparative examples 1 to 7 were made into addition type silicone rubbers with 80 parts by weight of vinylpolysiloxane, 20 parts by weight of alumina as an inorganic filler, 20 parts by weight of hydrosiloxane, 0.05 part by weight of chloroplatinic acid as a catalyst and 0.01 part of methylbutinol as an inhibitor, and the shear strength of each rubber composition after curing was tested in accordance with GB/T7124-2008.
And (3) testing conditions are as follows: curing at 25 ℃ for 72h and at 100 ℃ for 0.5 h; shear strength test the substrate was an aluminum sheet. The test results are shown in table 1:
TABLE 1
Figure BDA0002352061420000141
As can be seen from Table 1, the shear strength of the silicone rubber obtained by curing the tackifier provided by the invention at room temperature is better, wherein the mass ratio of octamethylcyclotetrasiloxane to tetramethyltetravinylcyclotetrasiloxane in example 4 is 50:1, which results in lower shear strength compared with other examples; as can be seen from comparison of examples 1 to 4, the optimum mass ratio of octamethylcyclotetrasiloxane to tetramethyltetravinylcyclotetrasiloxane is 20: 1; meanwhile, as can be seen from comparison of example 1 with comparative examples 1 to 3, the room temperature tackifier has the disadvantages that the raw materials for preparation are indispensable and must contain a vinyl group and a blocked amino group; as can be seen from the comparison of example 1 with comparative examples 4 and 5, increasing the amount of tetramethyltetravinylcyclotetrasiloxane used even if it exceeds octamethylcyclotetrasiloxane does not improve the performance of the tackifier; in comparative example 6, the amount of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane is increased, and the addition of the prepared tackifier to silicone rubber causes the silicone rubber to be incapable of being uncured, so that it can be seen from the comparison between example 1 and comparative examples 6 and 7 that the amount of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane to be used needs to be controlled within a reasonable range, otherwise the tackifying effect cannot be achieved.
In conclusion, the room-temperature tackifier with a tackifying effect and good tackifying property is obtained by controlling the components and the ratio of the raw materials, and the addition type silicone rubber prepared by the room-temperature tackifier has high shear strength after being cured at room temperature, wherein the shear strength is more than 0.5MPa and can reach 1.8MPa at most, and is even close to the shear strength after being heated and cured.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A room temperature tackifier, characterized in that the room temperature tackifier has a structure shown as formula I:
Figure FDA0002352061410000011
wherein m and n are each independently selected from integers greater than 0;
R1selected from C1-C10 alkylene, R2、R3、R4、R5、R6And R7The R is the same or different and is independently selected from any one of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl or C6-C30 aryl, and R4、R5、R6Or R7At least one of which is selected from C2-C10 alkenyl.
2. The room temperature adhesion promoter of claim 1, wherein the room temperature adhesion promoter has the formula:
Figure FDA0002352061410000012
wherein m and n are each independently selected from integers greater than 0;
preferably, m is selected from an integer from 1 to 100, preferably from 10 to 50;
preferably, n is selected from an integer from 1 to 20, preferably from 1 to 5.
3. A room temperature tackifier according to claim 1 or claim 2, wherein the room temperature tackifier has a viscosity of from 5 to 800 cps;
preferably, the room temperature tackifier has a weight average molecular weight of 888-500000, preferably 1000-5000.
4. A method of preparing a room temperature adhesion promoter as claimed in any one of claims 1 to 3, comprising the steps of:
will be provided with
Figure FDA0002352061410000021
Reacting to prepare the room-temperature tackifier;
preferably, the
Figure FDA0002352061410000022
Is octamethylcyclotetrasiloxane;
preferably, the
Figure FDA0002352061410000023
Is tetramethyl tetravinylcyclotetrasiloxane;
preferably, the
Figure FDA0002352061410000024
Is 1, 3-bis (3-aminopropyl) tetramethyldisiloxane.
5. The method of claim 4, comprising the steps of:
(1) to pair
Figure FDA0002352061410000025
Dehydrating;
(2) after dehydration
Figure FDA0002352061410000031
And the above-mentioned
Figure FDA0002352061410000032
And reacting under the action of a catalyst to obtain the room-temperature tackifier.
6. The method of claim 4 or 5, wherein the method comprises
Figure FDA0002352061410000033
The molar ratio of (1-1000):1, preferably (1-50):1, more preferably (5-20): 1;
preferably, the
Figure FDA0002352061410000034
The molar ratio of (1-10000):1, preferably (10-100): 1.
7. The method according to any one of claims 4 to 6, wherein the catalyst is selected from the group consisting of potassium hydroxide, tetramethylammonium hydroxide, and ammonia water;
preferably, the mass concentration of the ammonia water is 2-50%;
preferably, the catalyst is used in an amount of
Figure FDA0002352061410000041
0.0005-0.05 wt.% of the total weight.
8. The production method according to any one of claims 4 to 7, wherein the step (1) is a step of
Figure FDA0002352061410000042
The dehydration time is 30-120min respectively and the temperature is 50-80 ℃ respectively;
preferably, the reaction temperature in the step (2) is 80-120 ℃, and the reaction time is 1-6 h;
preferably, the step (2) also comprises removing low-boiling-point substances after the reaction is finished;
preferably, the temperature for removing the low-boiling-point substances is 120-180 ℃, and the time is 1-6 h.
9. The method of any one of claims 4-8, wherein the room temperature tackifier is prepared using octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, and 1, 3-bis (3-aminopropyl) tetramethyldisiloxane as raw materials, and the method comprises the steps of:
(1) dehydrating octamethylcyclotetrasiloxane at 50-80 deg.C for 30-120min, and dehydrating tetramethyltetravinylcyclotetrasiloxane at 50-80 deg.C for 30-120 min;
(2) mixing the dehydrated octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane with 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, reacting for 1-6h at 80-120 ℃ under the action of a catalyst, then heating to 120-180 ℃ and maintaining for 1-6h to remove low-boiling-point substances, thereby obtaining the room-temperature tackifier.
10. Use of a room temperature adhesion promoter according to any of claims 1 to 3 for the preparation of addition-type silicone rubbers.
CN201911419872.0A 2019-12-31 2019-12-31 Room-temperature tackifier and preparation method and application thereof Pending CN111072970A (en)

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CN104262631A (en) * 2014-09-29 2015-01-07 成都硅宝科技股份有限公司 Low molecular weight linear amino-terminated silicon oil and synthetic method thereof
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CN102775613A (en) * 2012-08-10 2012-11-14 广州天赐高新材料股份有限公司 Method for preparing alpha, omega-bis(aminopropyl)polydimethylsiloxane
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