CN112608476A - Anchoring agent and preparation method and application thereof - Google Patents
Anchoring agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN112608476A CN112608476A CN202011495828.0A CN202011495828A CN112608476A CN 112608476 A CN112608476 A CN 112608476A CN 202011495828 A CN202011495828 A CN 202011495828A CN 112608476 A CN112608476 A CN 112608476A
- Authority
- CN
- China
- Prior art keywords
- anchoring agent
- organosiloxane
- vinyl
- group
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004873 anchoring Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 37
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 32
- -1 alkoxy silane compound Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- 125000005375 organosiloxane group Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 4
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 229910000077 silane Inorganic materials 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 101710137710 Thioesterase 1/protease 1/lysophospholipase L1 Proteins 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000004754 hydrosilicons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011088 parchment paper Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- WJDGNMCHWAPAPY-UHFFFAOYSA-N propyl 3-trimethoxysilylprop-2-enoate Chemical compound CCCOC(=O)C=C[Si](OC)(OC)OC WJDGNMCHWAPAPY-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- 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
- C09J2483/00—Presence of polysiloxane
- C09J2483/005—Presence of polysiloxane in the release coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides a preparation method and application of an anchoring agent for an organic silicon release agent. The anchoring agent has a structure shown in a formula I. In the preparation process of the anchoring agent, polyorganosiloxane containing hydroxyl and an alkoxy silane compound containing vinyl groups are directly selected for condensation polymerization reaction, so that the generation of impurities in the reaction process can be reduced, the performance of the anchoring agent is further improved, and the prepared release agent has high adhesive force and low stripping performance when interacting with a substrate (such as paper and a polymer film), and the storage stability of the anchoring agent at room temperature can be improved.
Description
Technical Field
The invention belongs to the technical field of organic silicon, and particularly relates to an anchoring agent, and a preparation method and application thereof.
Background
The release agent is also called as an anti-sticking agent, is coated between a substrate and a pressure-sensitive adhesive to play a role in protecting an adhesive layer and preventing the adhesive layer from being polluted or losing efficacy before sticking other articles, and can be applied to the fields of labels, baking paper, self-sticking envelopes, sanitary products, electronic products and the like. The organic silicon release agent belongs to one of release agents, and can be divided into three types from the reaction mechanism: addition (i.e., platinum-catalyzed), condensation (organotin-catalyzed), and radiation curing (UV-light curing). From the aspect of product morphology, there are solvent type, solvent-free type and emulsion type. Of these, platinum-catalyzed products are the predominant products on the market today.
In order to improve the adhesion between the release agent and the substrate and reduce the probability of the release agent migrating to the pressure-sensitive adhesive, an anchoring agent needs to be added into the formula of the release agent.
The anchor agent is an essential component of the silicone release agent, and affects the release properties of the release film, such as the release force, residual adhesion rate, and the like, in addition to providing adhesion. The excellent anchoring agent must not deteriorate the anchoring property of the prepared release film to the substrate with time, and must also prevent the release film from obviously changing in peeling property during long-term storage. Therefore, the following conditions must be satisfied: firstly, the addition curing reaction is not influenced; secondly, the hydrolyzable free silicone oil can not be released to influence the viscosity of the pressure-sensitive adhesive; thirdly, toxic and odorous molecules are not released in the coating construction process.
Dongganbeili company discloses in patent CN106496565A that a siloxane containing hydrosilicon, unsaturated bond alkyl and acrylate functional group is used as a tackifier, and can obviously improve the bonding effect between silicone rubber and a resin base material difficult to bond. The company discloses another synthesis method of a tackifier in another patent CN108795319A, which comprises the steps of sequentially adding 3-glycidoxypropyltrimethoxysilane, 3-trimethoxylsilylacrylic propyl ester and vinyltriacetoxysilane into a reaction vessel, uniformly stirring, then adding deionized water, starting heating, after the heating temperature is raised to a certain temperature, stirring for a certain time at a constant temperature, then carrying out reduced pressure distillation, stopping distillation when no low-boiling-point substance flows out, and cooling to room temperature to obtain the organic silicon pressure-sensitive adhesive tackifier.
U.S. Pat. No. 5567764A discloses an organosiloxane containing vinyl and alkoxy groups as an additive to a release agent to enhance adhesion to a polyester film, however, the vinyl content affects adhesion to a substrate and thus does not meet the requirements of higher adhesion and lower peel force properties; the method for synthesizing the anchoring agent is disclosed in U.S. patent 2003/0088042A1, the anchoring agent prepared by cohydrolysis of vinyl silane and epoxy silane in several proportions can obviously improve the adhesive force of the release agent on paper and polyester films, similar to T-shaped silicon resin containing epoxy propyl and vinyl, but the T-shaped silicon resin can cause the increase of the peeling force of the release film, and is not beneficial to the preparation and storage stability of the release film with low peeling force; chinese patent CN105899617A prepared a water-based anchoring agent, which was improved in fixation property and stability by adding a surfactant, but its storage stability was still to be improved.
Therefore, it is required to develop an anchor agent that can improve both adhesion and peeling property between a release film and a substrate while having excellent storage stability.
Disclosure of Invention
The invention aims to overcome the defect that the adhesive force and the stripping performance between the existing release film and a substrate cannot be improved simultaneously, and provides an anchoring agent. The organic siloxane compound with the structure shown in the structural general formula 1 is used as an anchoring agent, is stable in storage at room temperature, has small influence on curing and stripping performance of a release film when being added into a release agent formula, is beneficial to obtaining low stripping force, and can not obviously change the stripping performance of the release film in a long-time storage process; meanwhile, the adhesive has good adhesive force with the base material, and can not release any toxic and harmful gas in the curing process of the release agent and release free silicone oil to influence the viscosity of the pressure-sensitive adhesive.
Another object of the present invention is to provide a method for preparing the anchoring agent.
The invention also aims to provide application of the anchoring agent in preparing a silicone release agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
an anchoring agent having a structure according to formula I:
wherein m and n are integers more than 2;
the molecular weight of the anchoring agent is 1000-9700; PDI is 1.7 to 2.5.
The anchoring agent is a functionalized organic siloxane compound, contains vinyl and epoxy groups, and directly selects polyorganosiloxane containing hydroxyl and an alkoxy silane compound containing vinyl groups to carry out polycondensation reaction in the preparation process, so that the generation of impurities in the reaction process can be reduced, the performance of the anchoring agent is further improved, and the prepared release agent has higher adhesive force and lower stripping performance when interacting with a substrate (such as paper and polymer film), and the storage stability of the anchoring agent at room temperature can be improved.
The preparation method of the anchoring agent comprises the following steps:
s1, carrying out polycondensation reaction on polysiloxane containing a silicon hydroxyl group and alkoxy organosiloxane compound containing a vinyl group to generate organosiloxane A containing the vinyl group and the silicon hydroxyl group;
s2, reacting organic siloxane A containing vinyl groups and silicon hydroxyl groups with hydrolyzable organic siloxane B containing epoxy groups under the action of a catalyst to obtain the anchoring agent;
preferably, the polyorganosiloxane containing the silicon hydroxyl group is hydroxyl silicone oil with the molecular weight of 200-7000.
More preferably, the polyorganosiloxane containing a silicon hydroxyl group is a hydroxyl silicone oil having a molecular weight of 1000 to 3000.
Preferably, the alkoxy organic siloxane compound containing vinyl groups is one or a combination of methyl vinyl dimethoxy silane and methyl vinyl diethoxy silane.
Preferably, in S1, the molar ratio of the polyorganosiloxane containing a silicon hydroxyl group and the alkoxyorganosiloxane compound containing a vinyl group, which are subjected to polycondensation reaction, is 1:1.
Preferably, step S1 may further include a catalyst, where the catalyst is a basic catalyst, and specifically is one or a combination of several of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ethylenediamine, ethanolamine, triethylamine, tetramethylammonium hydroxide, ammonium gum, alkali gum, an anionic resin, or a supported base.
Preferably, the catalyst is used in an amount of 0.1 to 0.03% by weight based on the total weight of the polyorganosiloxane containing a silicon hydroxyl group and the alkoxyorganosiloxane compound containing a vinyl group.
Preferably, the polycondensation reaction described in step S1 is carried out on dry N2Under protection, the aim is to prevent the interference of the water vapour in the humid air with the reaction.
Preferably, the temperature of the polycondensation reaction in the step S1 is 60-80 ℃.
Preferably, the time of the polycondensation reaction in the step S1 is 3-5 hours.
Preferably, after the polycondensation reaction in step S1, the method further comprises adjusting the pH to 7.
Preferably, the molecular weight of the organosiloxane A containing vinyl groups and silicon hydroxyl groups is 300-8000.
Further preferably, the molecular weight of the organic siloxane A containing vinyl groups and silicon hydroxyl groups is 1000-6000.
It has been found that the vinyl content of the organosiloxane a containing vinyl groups and silicon hydroxyl groups affects the performance of the anchoring agent. The content of vinyl is too high, the prepared anchoring agent is added into the organic silicon release agent, and the peeling force of the release film is larger; on the other hand, too low vinyl content may result in the decrease of the adhesion of the release agent to the substrate, for example, silicon loss occurs after the release film is stored for one month, which may affect the use.
Preferably, the hydrolysable organosiloxane B containing epoxy groups in step S2 is one or more of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane or 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane.
Researches find that the content of organic siloxane B in the anchoring agent influences the adhesion of the organic silicon release agent prepared by the anchoring agent to a substrate, and the higher the content of the organic siloxane B is, the better the adhesion of the organic silicon release agent to the substrate (such as paper or a PET polyester film) is.
Preferably, the mol ratio of the organic siloxane A to the organic siloxane B is 1: 0.5-2.
Further preferably, the molar ratio of organosiloxane a and organosiloxane B is 1: 1.25.
Preferably, the catalyst in step S2 is a solution of alkali dispersed in a compound, specifically one or a combination of several of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ethylenediamine, ethanolamine, triethylamine, tetramethylammonium hydroxide, ammonium gum, alkali gum, anionic resin or supported alkali solution.
Preferably, the catalyst is used in an amount of 0.01 to 0.03% by weight based on the total weight of the vinyl group-and silicon hydroxyl group-containing organosiloxane A and the epoxy group-containing hydrolyzable organosiloxane B.
Preferably, the reaction described in step S2 is carried out on dry N2Under protection, the aim is to prevent the interference of the water vapour in the humid air with the reaction.
Preferably, the temperature of the reaction in the step S2 is 60-80 ℃.
Preferably, the reaction time in step S2 is 3 to 5 hours.
Preferably, after the reaction in step S2 is finished, the method further comprises adjusting the pH to 7.
The application of the anchoring agent in the preparation of the organic silicon release agent is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
the organic siloxane compound with the structure shown in the structural general formula 1 is used as an anchoring agent, is stable in storage at room temperature, has small influence on curing and stripping performance of a release film when being added into a release agent formula, is beneficial to obtaining low stripping force, and can not obviously change the stripping performance of the release film in a long-time storage process; meanwhile, the adhesive has good adhesive force with a base material, and can not release any toxic and harmful gas in the curing process of the release agent and release free silicone oil to influence the viscosity of the pressure-sensitive adhesive.
Drawings
FIG. 1 is a molecular weight distribution spectrum of the anchoring agent prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1
The invention prepares an anchoring agent, which is prepared according to the following method:
s1.190g (molecular weight 200, 0.95mol) of a double-end hydroxyl polysiloxane, 125.6g (0.95mol) of methyl vinyl dimethoxy silane and 0.094g of KOH react at 60 ℃ for 3h to obtain an organosiloxane A containing a vinyl group and a silicon hydroxyl group, wherein the molecular weight is 510, and the PDI is 1.83;
s2.145.2g (0.28mol) of the organosiloxane A from S1, 82.7g (0.35mol) of 3- (2, 3-glycidoxy) propyltrimethoxysilane and 0.068g of KOH were reacted at 60 ℃ for 3h to give an anchor having a molecular weight of 1123 and a PDI of 1.73.
Example 2
The invention prepares an anchoring agent, which is prepared according to the following method:
s1.150g (molecular weight is 7000, 0.021mol) of double-end hydroxyl polysiloxane, 2.77g (0.021mol) of methyl vinyl dimethoxy silane and 0.045g of KOH react for 3h at 60 ℃ to obtain the organic siloxane A containing vinyl groups and silicon hydroxyl groups, wherein the molecular weight is 7700, and the PDI is 1.87;
s2.120g (0.015mol) of the organosiloxane A from S1, 5.42g (0.019mol) of 3- (2, 3-glycidoxy) propyltriethoxysilane and 0.0037g of KOH were reacted at 60 ℃ for 3 hours to give an anchor having a molecular weight of 8312 and a PDI of 1.77.
Example 3
The invention prepares an anchoring agent, which is prepared according to the following method:
s1.300g (molecular weight 200, 1.5mol) of a bishydroxy polysiloxane, 240.4g (1.5mol) of methylvinyldiethoxysilane and 0.16g of KOH were reacted at 60 ℃ for 3h to give an organosiloxane A containing a vinyl group and a silicon hydroxyl group and having a molecular weight of 552 and a PDI of 1.91;
s2.180g (0.326mol) of the organosiloxane A from S1, 100.4g (0.408mol) of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane and 0.084g of KOH were reacted at 60 ℃ for 3h to give an anchor having a molecular weight of 1240 and a PDI of 1.81.
Example 4
The invention prepares an anchoring agent, which is prepared according to the following method:
s1.500g (molecular weight 7000, 0.07mol) of a double-terminal hydroxyl polysiloxane, 11.22g (0.07mol) of methylvinyldiethoxysilane and 0.15g of KOH react at 60 ℃ for 3h to obtain an organosiloxane A containing a vinyl group and a silicon hydroxyl group, the molecular weight of which is 7800 and the PDI of which is 1.97;
s2.230g (0.029mol) of the organosiloxane A from S1, 7.99g (0.036mol) of 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and 0.071g of KOH are reacted at 60 ℃ for 3h to give an anchor having a molecular weight of 9659 and a PDI of 2.11.
Example 5
The preparation method of the present example is different from that of example 1 in that:
in step S1, the reaction time is 5h, and the organosiloxane A containing vinyl groups and silicon hydroxyl groups and having the molecular weight of 1000 and the PDI of 1.83 is prepared;
in step S2, 145.2g (0.145mol) of the organosiloxane A from S1, 42.8g (0.18mol) of 3- (2, 3-glycidoxy) propyltrimethoxysilane and 0.056g of KOH were reacted at 60 ℃ for 5h to give an anchor having a molecular weight of 1600 and a PDI of 1.81.
Example 6
The preparation method of the present example is different from that of example 1 in that:
in step S1, the reaction temperature is 80 ℃, and the organosiloxane A containing vinyl groups and silicon hydroxyl groups, with the molecular weight of 400 and the PDI of 1.85, is prepared;
s2.112g (0.28mol) of the obtained organosiloxane A from S1, 82.7g (0.35mol) of 3- (2, 3-glycidoxy) propyltrimethoxysilane and 0.058g of KOH were reacted at 60 ℃ for 3 hours to obtain an anchoring agent with molecular weight 1052 and PDI of 1.76.
Example 7
The preparation method of the present example is different from that of example 1 in that:
in step S1, the amount of catalyst KOH was 0.31g, and organosiloxane a containing a vinyl group and a silicon hydroxyl group and having a molecular weight of 1600 and a PDI of 1.83 was prepared;
in step S2, 145.2g (0.09mol) of the organosiloxane A from S1, 26.8g (0.11mol) of 3- (2, 3-glycidoxy) propyltrimethoxysilane and 0.017g of KOH were reacted at 60 ℃ for 3 hours to give an anchor having a molecular weight of 2107 and a PDI of 1.78.
Comparative example 1
The comparative example is prepared by taking hydroxyl-terminated dimethyl and methyl vinyl siloxane, beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane and vinyl dimethoxy siloxy-terminated polydimethylsiloxane as raw materials according to the preparation method of the anchoring agent in Chinese patent CN 105899617A.
Comparative example 2
A commercially available Dow Syl-Off DC 297 anchor was selected for this comparative example.
Performance testing
18.9g of a silicone oil having a viscosity of 590mPa.s, 0.334g of a poly (methylhydrogen) silane crosslinking agent, and 2.0g of a solution (1% concentration) of dimethyl maleate hexanol as an inhibitor in 120# solvent oil were uniformly mixed, 0.2g of the anchor agent synthesized in the above examples and comparative examples was added with 13.3g of 120# solvent oil and stirred uniformly, and finally 0.6g of Karster td platinum catalyst (Pt content 5000PPM) was added thereto, and after mixing and stirring uniformly, a 2 μm bar was disposed on a 5c PET polyester film of east China medical science, and the bar was drawn on the polyester film at a rate of 900mm/min, assuming that the dry silicon was 0.93g/m2. Curing for 30s at 150 ℃ by using a hot air drying oven to obtain the base material coated with the release agent. Laminating the cured PET release film with a TESA 7475 adhesive tape, attaching 6 sample strips, placing two sample strips in an air-conditioned room with the temperature of 25 ℃ and the humidity of 50% for 20h, aging the other two sample strips in an aging oven with the temperature of 70 ℃ and the humidity of 50% for 20h, and storing the rest 2 sample strips in an open atmospheric environment for 1 month. The test method of the peeling force refers to the test method of the peeling strength of the adhesive tape of GB/T2972-2014. And after the peeling force test is finished, carrying out an adhesion test on the peeled release film. The adhesive force of the organic silicon release agent to the PET film is measured by 5 times of parallel finger friction of the same experimenter on the premise of force balance, so that the effect of the anchoring agent is judged.
The test results of the examples and comparative examples are detailed in table 1.
TABLE 1 Release Properties of the examples and comparative examples
NNN in table 1 indicates no contamination, no migration, no erasure; glass stability (peel force-peel force at room temperature 20 h)/peel force at room temperature 20h 100%.
As can be seen from the results in table 1, compared with the conventional dow Syl-Off DC 297 anchor and the anchor prepared by the conventional method, the peel stability at high temperature (70 ℃ for 20 hours) is improved by at least 63.40%, and the peel stability at normal temperature for a long time (1 month) is improved by at least 72.36%.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An anchoring agent having a structure according to formula I:
wherein m and n are integers more than 2;
the molecular weight of the anchoring agent is 1000-9700; PDI is 1.7 to 2.5.
2. The method for preparing the anchoring agent according to claim 1, comprising the steps of:
s1, carrying out polycondensation reaction on polysiloxane containing a silicon hydroxyl group and alkoxy organosiloxane compound containing a vinyl group to generate organosiloxane A containing the vinyl group and the silicon hydroxyl group;
s2, reacting organic siloxane A containing vinyl groups and silicon hydroxyl groups with hydrolyzable organic siloxane B containing epoxy groups under the action of a catalyst to obtain the anchoring agent.
3. The method according to claim 2, wherein the polyorganosiloxane containing a silicon hydroxyl group is a hydroxyl silicone oil having a molecular weight of 200 to 7000;
the alkoxy organic siloxane compound containing vinyl groups is one or a combination of several of methyl vinyl dimethoxy silane and methyl vinyl diethoxy silane;
the hydrolysable organic siloxane B containing the epoxy group is one or a combination of more of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane or 3- [ (2,3) -epoxypropoxy ] propylmethyldimethoxysilane.
4. The method according to claim 2, wherein the molar ratio of the organosiloxane A to the organosiloxane B is 1:0.5 to 2.
5. The method according to claim 2, wherein the organosiloxane A having a vinyl group and a silicon hydroxyl group has a molecular weight of 300 to 8000.
6. The method according to claim 2, wherein the catalyst in step S2 is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ethylenediamine, ethanolamine, triethylamine, tetramethylammonium hydroxide, ammonium gum, alkali gum, anionic resin, and supported alkali solution.
7. The method according to claim 2, wherein the catalyst is used in an amount of 0.01 to 2% by weight based on the total weight of the vinyl group-and silicon hydroxyl group-containing organosiloxane A and the epoxy group-containing hydrolyzable organosiloxane B.
8. The method according to claim 2, wherein the temperature of the reaction in step S1 is 60-80 ℃; the reaction temperature in the step S2 is 60-80 ℃.
9. The preparation method according to claim 2, wherein the reaction time in the step S1 is 3-5 h; the reaction time in the step S2 is 3-5 h.
10. Use of the anchoring agent according to claim 1 for the preparation of silicone release agents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011495828.0A CN112608476A (en) | 2020-12-17 | 2020-12-17 | Anchoring agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011495828.0A CN112608476A (en) | 2020-12-17 | 2020-12-17 | Anchoring agent and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112608476A true CN112608476A (en) | 2021-04-06 |
Family
ID=75240830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011495828.0A Pending CN112608476A (en) | 2020-12-17 | 2020-12-17 | Anchoring agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112608476A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113430860A (en) * | 2021-06-22 | 2021-09-24 | 惠州市永卓科技有限公司 | Medium-weight stripping force solvent-free release silicone oil and preparation method thereof |
| CN113755015A (en) * | 2021-10-08 | 2021-12-07 | 美信新材料股份有限公司 | Anti-falling heat-conducting gel, preparation method thereof and electronic instrument |
| CN114163645A (en) * | 2021-12-09 | 2022-03-11 | 万华化学集团股份有限公司 | Anchoring agent and preparation method and application thereof |
| CN114196021A (en) * | 2022-01-06 | 2022-03-18 | 万华化学集团股份有限公司 | Anchoring agent and preparation method and application thereof |
| CN114874700A (en) * | 2022-04-25 | 2022-08-09 | 杭州崇耀科技发展有限公司 | Environment-friendly release agent and preparation method thereof |
| CN114891224A (en) * | 2022-05-16 | 2022-08-12 | 江苏至昕新材料有限公司 | High-adhesion anchoring agent and preparation method and application thereof |
| CN115975428A (en) * | 2021-10-15 | 2023-04-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101517002A (en) * | 2006-08-14 | 2009-08-26 | 陶氏康宁公司 | Silicone release coating compositions |
| CN105899617A (en) * | 2013-11-26 | 2016-08-24 | 道康宁(中国)投资有限公司 | Anchorage additive emulsion for silicone release coating composition |
| US20170233612A1 (en) * | 2014-10-16 | 2017-08-17 | Dow Corning Corporation | Silicone composition and a pressure sensitive adhesive film having a pressure sensitive adhesive layer made from the composition |
| CN108329477A (en) * | 2018-02-28 | 2018-07-27 | 华南理工大学 | A kind of organic silicon rigidity-increasing stick and preparation method thereof |
| WO2020000387A1 (en) * | 2018-06-29 | 2020-01-02 | Dow Silicones Corporation | Anchorage additive and methods for its preparation and use |
| WO2020131367A1 (en) * | 2018-12-21 | 2020-06-25 | Dow Silicones Corporation | Polyfunctional organosiloxanes, compositions containing same, and methods for the preparation thereof |
-
2020
- 2020-12-17 CN CN202011495828.0A patent/CN112608476A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101517002A (en) * | 2006-08-14 | 2009-08-26 | 陶氏康宁公司 | Silicone release coating compositions |
| CN105899617A (en) * | 2013-11-26 | 2016-08-24 | 道康宁(中国)投资有限公司 | Anchorage additive emulsion for silicone release coating composition |
| US20160376475A1 (en) * | 2013-11-26 | 2016-12-29 | Dow Corning Corporation | Anchorage additive emulsion for silicone release coating composition |
| US20170233612A1 (en) * | 2014-10-16 | 2017-08-17 | Dow Corning Corporation | Silicone composition and a pressure sensitive adhesive film having a pressure sensitive adhesive layer made from the composition |
| CN108329477A (en) * | 2018-02-28 | 2018-07-27 | 华南理工大学 | A kind of organic silicon rigidity-increasing stick and preparation method thereof |
| WO2020000387A1 (en) * | 2018-06-29 | 2020-01-02 | Dow Silicones Corporation | Anchorage additive and methods for its preparation and use |
| WO2020131367A1 (en) * | 2018-12-21 | 2020-06-25 | Dow Silicones Corporation | Polyfunctional organosiloxanes, compositions containing same, and methods for the preparation thereof |
Non-Patent Citations (3)
| Title |
|---|
| 郝晓鹏: ""不干标签用有机硅离型剂的应用"", 《浙江化工》 * |
| 陈正旺等: "LED 封装胶专用增粘剂的制备", 《有机硅材料》 * |
| 韩长日等主编: "《造纸用化学品生产工艺与技术》", 31 May 2019, 科学技术文献出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113430860A (en) * | 2021-06-22 | 2021-09-24 | 惠州市永卓科技有限公司 | Medium-weight stripping force solvent-free release silicone oil and preparation method thereof |
| CN113755015A (en) * | 2021-10-08 | 2021-12-07 | 美信新材料股份有限公司 | Anti-falling heat-conducting gel, preparation method thereof and electronic instrument |
| CN113755015B (en) * | 2021-10-08 | 2022-12-09 | 美信新材料股份有限公司 | Anti-drop heat-conducting gel, preparation method thereof and electronic instrument |
| CN115975428A (en) * | 2021-10-15 | 2023-04-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
| CN115975428B (en) * | 2021-10-15 | 2023-07-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
| CN114163645A (en) * | 2021-12-09 | 2022-03-11 | 万华化学集团股份有限公司 | Anchoring agent and preparation method and application thereof |
| CN114163645B (en) * | 2021-12-09 | 2023-01-13 | 万华化学集团股份有限公司 | Anchoring agent and preparation method and application thereof |
| CN114196021A (en) * | 2022-01-06 | 2022-03-18 | 万华化学集团股份有限公司 | Anchoring agent and preparation method and application thereof |
| CN114874700A (en) * | 2022-04-25 | 2022-08-09 | 杭州崇耀科技发展有限公司 | Environment-friendly release agent and preparation method thereof |
| CN114891224A (en) * | 2022-05-16 | 2022-08-12 | 江苏至昕新材料有限公司 | High-adhesion anchoring agent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112608476A (en) | Anchoring agent and preparation method and application thereof | |
| CN109880523B (en) | High-temperature-resistant low-transfer organic silicon release agent and preparation method thereof | |
| CA1261509A (en) | Coating method and silicone composition for psa release coating | |
| US4743474A (en) | Coating process and moisture-curable organopolysiloxane compositions therefor | |
| JP4906735B2 (en) | Method for preparing branched siloxane | |
| JP2665881B2 (en) | Long-chain α-acetylene alcohols as inhibitors of hydrosilylation reaction and their application in preparing stable curable silicone compositions | |
| US9562149B2 (en) | Silicone release coating compositions | |
| EP3275961B1 (en) | Laminate comprising release liner based on release agent composition for silicone adhesive | |
| EP1947133A1 (en) | Ultraviolet-curable silicone composition | |
| CN102344748A (en) | Solventless releaser composition for use with silicone pressure-sensitive adhesives and release liner | |
| CN101180343A (en) | Fluoroalkyl-silylated MQ resin and solvent-resistant pressure-sensitive adhesive composition containing it | |
| TWI534213B (en) | Addition curable silicone emulsion release composition and release film | |
| TWI814070B (en) | Silicone-based coating composition and silicone-based release film including the same | |
| CN114058290B (en) | Solvent-free organosilicon release agent with ultralow release force and preparation method thereof | |
| TWI374173B (en) | ||
| CN114891224A (en) | High-adhesion anchoring agent and preparation method and application thereof | |
| JP3751186B2 (en) | Silicone adhesive composition | |
| CN104817702A (en) | Spherical dendritic organic silicon macromolecule, preparation method thereof and application | |
| JP2012246359A (en) | Silicone composition for release paper or release film | |
| JP3024445B2 (en) | Silicone composition for release agent and release paper | |
| EP4310119A1 (en) | Silicone-based composition and cured product thereof | |
| US4530882A (en) | Coating method and silicone composition for PSA release coating | |
| WO2002006404A1 (en) | Silicone release coating compositions | |
| WO2013179896A1 (en) | Adhesive tape or sheet and method for manufacturing same | |
| JPS58142935A (en) | Primer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210406 |