CN116199819A - Acrylic ester polymer for pressure-sensitive adhesive, and preparation method and application thereof - Google Patents
Acrylic ester polymer for pressure-sensitive adhesive, and preparation method and application thereof Download PDFInfo
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- CN116199819A CN116199819A CN202211722501.1A CN202211722501A CN116199819A CN 116199819 A CN116199819 A CN 116199819A CN 202211722501 A CN202211722501 A CN 202211722501A CN 116199819 A CN116199819 A CN 116199819A
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 47
- 229920006222 acrylic ester polymer Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 90
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 88
- 239000003999 initiator Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000058 polyacrylate Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000013557 residual solvent Substances 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 7
- 238000010189 synthetic method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a synthetic method of an acrylic ester polymer for pressure-sensitive adhesive. The method comprises the following steps: 1) Carrying out a first-stage polymerization reaction on a first part of polymerization raw materials in a reaction kettle, wherein the first part of polymerization raw materials consist of a first part of hard monomers, a first part of soft monomers, a first part of functional monomers, a first part of initiator and a first part of solvent, and the mass concentration of the first part of monomers is 38.0-42.0% in total; 2) Dripping a second part of polymerization raw materials into the reaction kettle, and carrying out a second-stage polymerization reaction, wherein the second part of polymerization raw materials comprise residual hard monomers, residual soft monomers, residual functional monomers, a second part of initiator and a second part of solvent, and the mass concentration of the second part of monomers is 33.0% -37.0%; 3) And (3) dropwise adding the rest of the initiator and the rest of the solvent into the reaction kettle, and carrying out a third-stage polymerization reaction. The method can prepare the polymer with high molecular weight and narrow distribution.
Description
Technical Field
The invention relates to an acrylic ester polymer for pressure-sensitive adhesive, a preparation method and application thereof.
Background
Pressure-sensitive adhesives are a class of viscoelastic soft materials that are tacky at room temperature and adhere to the surface of an adherend under the action of an external force such as finger pressure. The method not only has wide application in industry, agriculture, traffic and medical treatment, but also has great application potential in military, aerospace and other aspects. Among them, acrylic pressure-sensitive adhesives (Acrylic Pressure Sensitive Adhesives, APSP) are the most widely used pressure-sensitive adhesives at present because of their excellent adhesive property, oxidation resistance, low synthetic cost, high transparency and other advantages.
In order to meet the demands of different industries on pressure-sensitive adhesives, APSA can be classified into emulsion type, organic solvent type, hot melt type and radiation curing type according to different synthetic production processes. Among them, solvent-based and emulsion-based APSA still occupy a major market share, and although organic solvent-based APSA is not environmentally friendly, it still occupies an irreplaceable position.
The heat resistance, flexibility, etc. of the pressure-sensitive adhesive are still further improved, and the initial tackiness, holding tackiness and cohesive strength of the pressure-sensitive adhesive are still required to be strictly controlled in some specific fields such as the field of daily electronics, and these properties of the pressure-sensitive adhesive are closely related to the physicochemical properties of the host resin of the pressure-sensitive adhesive, such as to the molecular weight of the host resin and its distribution. Therefore, it is necessary to investigate how to prepare a pressure-sensitive adhesive main body resin having a high molecular weight and a narrow molecular weight distribution.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides an improved acrylic ester polymer for pressure-sensitive adhesive, which has high molecular weight and narrow molecular weight distribution, and can improve the performance of the pressure-sensitive adhesive when being applied to the pressure-sensitive adhesive.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing an acrylate polymer for a pressure-sensitive adhesive, the method comprising the steps of: 1) Carrying out first-stage polymerization reaction on a first part of polymerization raw materials in a reaction kettle, wherein the first part of polymerization raw materials consist of a first part of hard monomers, a first part of soft monomers, a first part of functional monomers, a first part of initiator and a first part of solvent, and the mass concentration of the first part of hard monomers, the first part of soft monomers and the first part of functional monomers is 38.0-42.0% in total; 2) Dripping a second part of polymerization raw materials into the reaction kettle, and performing a second-stage polymerization reaction, wherein the second part of polymerization raw materials comprise residual hard monomers, residual soft monomers, residual functional monomers, a second part of initiator and a second part of solvent, and the mass concentration of the residual hard monomers, the residual soft monomers and the residual functional monomers is 33.0-37.0% in total; 3) And (3) dropwise adding the rest of the initiator and the rest of the solvent into the reaction kettle, and carrying out a third-stage polymerization reaction to obtain the acrylic ester polymer for the pressure-sensitive adhesive after the reaction is finished.
In some embodiments, after the residual initiator and residual solvent are added dropwise, all of the monomer added dropwise into the reaction vessel is 28.0% -32.0% of the total mass of the monomer and all of the solvent added dropwise.
In some embodiments, the mass concentration of the first partially hard monomer, the first partially soft monomer, and the first partially functional monomer add up to 39.8% to 40.2%.
Preferably, the mass concentration of the first part hard monomer, the first part soft monomer and the first part functional monomer is 40.0% in total.
In some embodiments, the mass concentrations of the remaining hard monomer, the remaining soft monomer, and the remaining functional monomer add up to 34.8% to 35.2%.
Preferably, the mass concentration of the remaining hard monomer, the remaining soft monomer and the remaining functional monomer is 35.0% in total.
In some embodiments, after the addition of the remaining initiator and the remaining solvent, all of the monomer added dropwise into the reaction vessel is 29.8% to 30.2% of the total mass of the monomer and all of the solvent added dropwise.
Preferably, after the residual initiator and the residual solvent are added dropwise, the total amount of monomer added dropwise into the reaction vessel is 30.0% of the total mass of the monomer and the total amount of solvent added dropwise.
In some embodiments, the temperature of the first stage polymerization reaction is 59 to 61 ℃.
In some embodiments, the temperature of the second stage polymerization reaction is 59 to 61 ℃.
In some embodiments, the temperature of the third stage polymerization reaction is 59 to 61 ℃.
The too high or too low temperature of the polymerization reaction in the first stage, the second stage and the third stage is not beneficial to the control of the molecular weight and the distribution of the acrylic ester polymer.
In some embodiments, the first stage polymerization reaction time is from 1.5 to 2.5 hours.
In some embodiments, the second stage polymerization reaction is for a period of time ranging from 2.5 to 3.5 hours.
In some embodiments, the third stage polymerization reaction is for a period of time ranging from 1.5 to 2.5 hours.
In some embodiments, the first stage polymerization, the second stage polymerization, and the third stage polymerization are all performed with agitation at a rate of 170 to 190r/min.
Preferably, the first stage polymerization reaction, the second stage polymerization reaction and the third stage polymerization reaction are all carried out under stirring, and the stirring speed is 180r/min.
In some embodiments, in step 2), the time of the dropping is 20 to 40min and the rate of the dropping is 13 to 17ml/min. In the second stage polymerization reaction, the dropping speed is too slow or too fast, which is not beneficial to the control of the molecular weight and the distribution of the acrylic ester polymer.
In some embodiments, the first stage polymerization, the second stage polymerization, and the third stage polymerization are all performed under controlled water bath temperature, the initial water bath temperature is set to 59-61 ℃, when the first stage polymerization is performed for 30min, the water bath temperature is set to 55-57 ℃ for 10min, and then the water bath temperature is set to 59-61 ℃ again.
Preferably, the first stage polymerization reaction, the second stage polymerization reaction and the third stage polymerization reaction are all carried out under the control of the water bath, the initial temperature of the water bath is set to 60 ℃, when the first stage polymerization reaction is carried out for 30min, the water bath temperature is set to 56 ℃ for 10-15min, and then the water bath temperature is set to 60 ℃ again. When the polymerization reaction in the first stage is carried out for 30min, the heat release of the polymerization reaction system is faster, so that the local material temperature in the reaction kettle is easily overhigh, and the control of the molecular weight distribution of the polymer is not facilitated. At the moment, the water bath temperature is properly reduced, so that the temperature of the polymerization raw material in the reaction kettle can be relieved from rising too fast, and the stable polymerization is facilitated.
In some embodiments, the hard monomer is methyl methacrylate.
In some embodiments, the soft monomer is selected from butyl acrylate or isooctyl acrylate.
In some embodiments, the functional monomer is selected from hydroxyethyl acrylate or hydroxybutyl acrylate.
In some embodiments, the initiator is azobisisoheptonitrile.
In some embodiments, the solvent is ethyl acetate.
In some embodiments, the molar ratio of the first portion of hard monomer, the first portion of soft monomer, the first portion of functional monomer, and the first portion of initiator is from 2 to 40:270-4100:2-40:1.
preferably, the molar ratio of the first part hard monomer, the first part soft monomer, the first part functional monomer and the first part initiator is 36.5:4040:36.5:1.
in some embodiments, the molar ratio of the remaining hard monomer, remaining soft monomer, remaining functional monomer, and second portion initiator is from 30 to 42:4000-4100:30-42:1.
preferably, the molar ratio of the remaining hard monomer, remaining soft monomer, remaining functional monomer and second portion of initiator is 35.8:4034:35.8:1.
in some embodiments, the mass of the remaining initiator comprises 18-22% of the combined mass of the first portion of initiator and the second portion of initiator.
Preferably, the mass of the remaining initiator is 20% of the combined mass of the first and second portions of initiator.
The invention also provides the acrylic ester polymer for the pressure-sensitive adhesive, which is prepared by the preparation method, and has the molecular weight of more than 20 ten thousand and the molecular weight distribution of less than 1.74.
The invention also provides application of the acrylate polymer for the pressure-sensitive adhesive in pressure-sensitive adhesives.
Compared with the prior art, the invention has the following advantages:
according to the invention, the monomers, the initiator and the solvent are fed in batches, part of the monomers, part of the initiator and part of the solvent are fed in the first and second feeding processes, and the rest of the initiator and the rest of the solvent are fed in the third feeding process, so that the mass concentration of the monomers in the first and second feeding processes and the dosage of the diluent added in the third stage are controlled, and the polymerization reaction in the three stages is correspondingly carried out, so that the molecular weight and the distribution of the acrylate polymer can be effectively controlled, and the acrylate polymer with high molecular weight and narrow molecular weight distribution can be obtained.
According to the invention, the temperature of the polymerization reaction system is controlled by adopting the water bath, when the polymerization reaction in the first stage is carried out for 30min, the water bath temperature is slightly reduced by 10-15min, the local polymerization raw material temperature which is caused by the heat release of the polymerization reaction is relieved, and the molecular weight distribution of the acrylic ester polymer can be well controlled.
The invention can improve the molecular weight and the distribution of the polymer by controlling the rate of dripping the polymerization raw material into the reaction kettle during the second-stage polymerization reaction.
The acrylate polymer for the pressure-sensitive adhesive prepared by the invention is colorless and transparent in appearance, does not change color after long-time exposure to sunlight, and is not easy to age. The acrylic ester polymer for the pressure-sensitive adhesive has high molecular weight, narrow molecular weight distribution and lower monomer residue.
Drawings
FIG. 1 is a nuclear magnetic resonance chart of the acrylic polymer for pressure-sensitive adhesive prepared in example 1;
FIG. 2 is a GPC chart of an acrylic polymer for pressure sensitive adhesive prepared in example 1.
Detailed Description
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment provides an acrylic ester polymer for pressure-sensitive adhesive, which comprises the following preparation steps:
firstly, the tightness of the device and whether the devices and equipment of the reaction kettle operate normally were checked, and after confirming that the devices and equipment have no problems, various raw materials are weighed correspondingly according to the amounts shown in the following table 1.
Methyl methacrylate MMA, butyl acrylate BA, hydroxybutyl acrylate HBA, solvent ethyl acetate EA and initiator azobisisoheptonitrile ABVN in the first polymerization stage were charged into the reaction vessel and the material in the second polymerization stage was weighed according to the amounts in Table 1 below: methyl methacrylate, butyl acrylate, hydroxybutyl acrylate, ethyl acetate and an initiator azo-diisoheptonitrile are added into a constant pressure dropping funnel, and the constant pressure dropping funnel is arranged on one port of the reaction kettle; nitrogen was simultaneously bubbled into the autoclave and constant pressure dropping funnel for one hour.
Placing the reaction kettle in a circulating water bath, arranging a thermometer in the reaction kettle, starting an external heating device to heat, and starting the circulating water bath; when the temperature in the reaction kettle reaches 60 ℃, the first-stage polymerization reaction is started, the reaction is carried out under stirring, the stirring speed is 180r/min, when the reaction reaches 30min, the circulating water bath is cooled to 56 ℃, the circulating water bath is continuously heated to 60 ℃ after the reaction lasts for 10min, the first-stage polymerization reaction is continuously carried out, and the total duration of the first-stage polymerization reaction is 2 hours.
And (3) dropwise adding materials in the second polymerization stage into the reaction kettle from a constant-pressure dropping funnel, performing the second-stage polymerization reaction, wherein the dropwise adding rate is 15ml/min, continuing the reaction after the dropwise adding is finished, controlling the temperature in a circulating water bath and the temperature in the reaction kettle to be 60 ℃ in the whole process, performing the reaction under stirring, and the stirring rate is 180r/min, wherein the total duration of the second-stage polymerization reaction is 3 hours.
And (3) dropwise adding materials in a third polymerization stage, including ethyl acetate and an initiator azo-diisoheptonitrile, wherein the materials are specifically shown in the following table 1, continuing to react after the dropwise adding is finished, controlling the temperature in a circulating water bath and the temperature in the reaction kettle to be 60 ℃ in the whole process, and stirring the materials at a stirring speed of 180r/min, wherein the total duration of the polymerization reaction in the third stage is 2 hours.
And after the polymerization is finished, discharging the polymer from a discharge hole of the reaction kettle to obtain the acrylic ester polymer. The nuclear magnetic test was performed using deuterated chloroform, and the results are shown in fig. 1, and successful synthesis of the polymer can be seen. GPC measurement showed that the number average molecular weight of the polymer was 47 million, and the molecular weight distribution PDI was 1.56, as shown in FIG. 2.
Example 2
This example provides an acrylic polymer for pressure-sensitive adhesive, which is basically the same as example 1 in its preparation steps, except that: the amounts of raw materials added at each polymerization stage were slightly different, and the molecular weights and the distribution of the finally obtained acrylate polymers are shown in Table 1 below.
Example 3
This example provides an acrylic polymer for pressure-sensitive adhesive, which is basically the same as example 1 in its preparation steps, except that: the amounts of raw materials added at each polymerization stage were slightly different, and the molecular weights and the distribution of the finally obtained acrylate polymers are shown in Table 1 below.
Table 1 materials added at each polymerization stage of each example
Comparative example 1
This comparative example provides an acrylic polymer for pressure-sensitive adhesive, which is basically the same as in example 1, except that: the mass concentration of the monomers in the first polymerization stage was varied and the feed to each polymerization stage was as shown in Table 1.
Comparative example 2
This comparative example provides an acrylic polymer for pressure-sensitive adhesive, which is basically the same as in example 1, except that: the mass concentration of the monomers in the first polymerization stage was varied and the feed to each polymerization stage was as shown in Table 1.
Comparative example 3
This comparative example provides an acrylic polymer for pressure-sensitive adhesive, which is basically the same as in example 1, except that: the dropping rate of the material in the second polymerization stage was 43ml/min, and as a result, the molecular weight of the obtained acrylate polymer was 35W and PDI was 1.82.
Comparative example 4
This comparative example provides an acrylic polymer for pressure-sensitive adhesive, which is basically the same as in example 1, except that: the dropping rate of the material in the second polymerization stage was 7ml/min, and as a result, the molecular weight of the obtained acrylate polymer was 20W and PDI was 2.2.
Comparative example 5
This comparative example provides an acrylic polymer for pressure-sensitive adhesive, which is basically the same as in example 1, except that: the temperature of the circulating water bath at the time of the first-stage polymerization was set at 60℃at all times, and as a result, the molecular weight of the resulting acrylate polymer was 15W and the PDI was 2.5.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (10)
1. A method for preparing an acrylate polymer for a pressure-sensitive adhesive, characterized in that the method comprises the following steps: 1) Carrying out first-stage polymerization reaction on a first part of polymerization raw materials in a reaction kettle, wherein the first part of polymerization raw materials consist of a first part of hard monomers, a first part of soft monomers, a first part of functional monomers, a first part of initiator and a first part of solvent, and the mass concentration of the first part of hard monomers, the first part of soft monomers and the first part of functional monomers is 38.0-42.0% in total; 2) Dripping a second part of polymerization raw materials into the reaction kettle, and performing a second-stage polymerization reaction, wherein the second part of polymerization raw materials comprise residual hard monomers, residual soft monomers, residual functional monomers, a second part of initiator and a second part of solvent, and the mass concentration of the residual hard monomers, the residual soft monomers and the residual functional monomers is 33.0-37.0% in total; 3) And (3) dropwise adding the rest of the initiator and the rest of the solvent into the reaction kettle, and carrying out a third-stage polymerization reaction to obtain the acrylic ester polymer for the pressure-sensitive adhesive after the reaction is finished.
2. The method for producing an acrylic acid ester polymer for pressure-sensitive adhesive according to claim 1, characterized in that: after the residual initiator and the residual solvent are added dropwise, the total monomer added dropwise into the reaction kettle accounts for 28.0-32.0% of the total mass of the monomer and the total solvent added dropwise.
3. The method for producing an acrylic acid ester polymer for pressure-sensitive adhesive according to claim 1, characterized in that: the mass concentration of the first part of hard monomer, the first part of soft monomer and the first part of functional monomer is 39.8-40.2%; and/or the mass concentrations of the remaining hard monomer, the remaining soft monomer, and the remaining functional monomer add up to 34.8% -35.2%; and/or after the residual initiator and the residual solvent are added dropwise, the total monomer added dropwise into the reaction kettle accounts for 29.8-30.2% of the total mass of the monomer and the total solvent added dropwise.
4. The method for producing an acrylic acid ester polymer for pressure-sensitive adhesive according to claim 1, characterized in that: the temperature of the first-stage polymerization reaction is 59-61 ℃; and/or, the temperature of the second stage polymerization reaction is 59-61 ℃; and/or, the temperature of the third stage polymerization reaction is 59-61 ℃; and/or the time of the first stage polymerization reaction is 1.5-2.5h; and/or the second stage polymerization reaction time is 2.5-3.5h; and/or the time of the third stage polymerization reaction is 1.5-2.5h.
5. The method for producing an acrylic acid ester polymer for pressure-sensitive adhesive according to claim 1, characterized in that: the first-stage polymerization reaction, the second-stage polymerization reaction and the third-stage polymerization reaction are all carried out under stirring, and the stirring speed is 170-190r/min; and/or in the step 2), the dripping time is 20-40min, and the dripping speed is 13-17ml/min.
6. The method for producing an acrylic acid ester polymer for pressure-sensitive adhesive according to claim 1, characterized in that: the first stage polymerization reaction, the second stage polymerization reaction and the third stage polymerization reaction are all carried out under the water bath temperature control, the initial temperature of the water bath is set to be 59-61 ℃, when the first stage polymerization reaction is carried out for 30min, the water bath temperature is set to be 55-57 ℃ for 10-15min, and then the water bath temperature is set to be 59-61 ℃ again.
7. The method for producing an acrylic acid ester polymer for pressure-sensitive adhesive according to claim 1, characterized in that: the hard monomer is methyl methacrylate; and/or the soft monomer is selected from butyl acrylate or isooctyl acrylate; and/or the functional monomer is selected from hydroxyethyl acrylate or hydroxybutyl acrylate; and/or, the initiator is azo-diisoheptonitrile; and/or the solvent is ethyl acetate.
8. The method for producing an acrylic acid ester polymer for pressure-sensitive adhesive according to claim 1, characterized in that: the mole ratio of the first part of hard monomer, the first part of soft monomer, the first part of functional monomer and the first part of initiator is 2-40:270-4100:2-40:1, a step of; and/or the molar ratio of the remaining hard monomer, the remaining soft monomer, the remaining functional monomer and the second portion of initiator is 30-42:4000-4100:30-42:1, a step of; and/or, the mass of the remaining initiator is 18-22% of the combined mass of the first portion of initiator and the second portion of initiator.
9. An acrylate polymer for pressure sensitive adhesive, characterized in that: the acrylic ester polymer for the pressure-sensitive adhesive is prepared by the preparation method of any one of claims 1-8, and has a molecular weight of more than 20 ten thousand and a molecular weight distribution of less than 1.7.
10. Use of the acrylate polymer for pressure-sensitive adhesive as claimed in claim 9 for pressure-sensitive adhesive.
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Citations (4)
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| CN105482748A (en) * | 2015-12-25 | 2016-04-13 | 何明辉 | High-temperature-resistant solvent-type acrylate pressure-sensitive adhesive and preparation method thereof, and pressure-sensitive adhesive tape |
| CN106432582A (en) * | 2016-08-30 | 2017-02-22 | 泰兴联创绝缘材料有限公司 | Method for polymerizing pressure-sensitive adhesive by using reactant concentration to control molecular weight distribution |
| CN106795410A (en) * | 2014-12-16 | 2017-05-31 | 株式会社Lg化学 | Pressure-sensitive adhesive composition |
| CN113549413A (en) * | 2021-08-16 | 2021-10-26 | 江苏耐斯数码科技股份有限公司 | Benzene-free solvent-type peelable pressure-sensitive adhesive and preparation method thereof |
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| CN106795410A (en) * | 2014-12-16 | 2017-05-31 | 株式会社Lg化学 | Pressure-sensitive adhesive composition |
| CN105482748A (en) * | 2015-12-25 | 2016-04-13 | 何明辉 | High-temperature-resistant solvent-type acrylate pressure-sensitive adhesive and preparation method thereof, and pressure-sensitive adhesive tape |
| CN106432582A (en) * | 2016-08-30 | 2017-02-22 | 泰兴联创绝缘材料有限公司 | Method for polymerizing pressure-sensitive adhesive by using reactant concentration to control molecular weight distribution |
| CN113549413A (en) * | 2021-08-16 | 2021-10-26 | 江苏耐斯数码科技股份有限公司 | Benzene-free solvent-type peelable pressure-sensitive adhesive and preparation method thereof |
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