A polymer for cross-linked end-side long carbon chain polyurethane non-silicon release agent, release agent and preparation method thereof

Abstract

The present invention proposes a polymer of a cross-linked end-side long carbon chain polyurethane non-silicon release agent, a release agent and a preparation method thereof, wherein the polymer of the release agent is polymerized by terminal hydroxyl polybutadiene, diisocyanate and alkane chain extender under the catalytic action of a catalyst to generate a polymer, and the polymer is polymerized and cured under the action of a multifunctional vinyl monomer and a catalyst to obtain a release agent. The present invention provides more cross-linking sites by using terminal hydroxyl polybutadiene containing unsaturated carbon-carbon double bonds, thereby ensuring the weather resistance and temperature resistance of the release agent, and at the same time uses an alkane chain extender to provide a non-polar segment in the side chain to achieve good release performance of the release agent. The resulting non-silicon release agent has excellent thermal stability and release performance.

Description

Technical Field

[0001] The invention relates to the technical field of release agents, and in particular to a polymer for a cross-linked end-side long carbon chain polyurethane non-silicon release agent, a release agent and a preparation method thereof. Background Art

[0002] Release film refers to a film with good separation performance on the surface. It is a functional film material obtained by coating a release agent on various base films and then curing by heat or UV light. Usually, its special molecular structure gives it low surface free energy and low surface adhesion strength, thus showing excellent separation performance. The release agents currently used are mainly divided into silicone release agents, fluorine release agents and non-silicone release agents. Among them, silicone release agents are widely used in various fields such as automobiles, electronics, and aviation due to their good transparency, convenient peeling force adjustment, good isolation performance, and good high temperature resistance and solvent resistance. Fluorine release agents are also widely used in silicone pressure-sensitive adhesives, aerospace and other fields due to their unique high temperature resistance and low peeling force.

[0003] With the rapid development of the electronics industry, the requirements for release films are getting higher and higher. Some electronic products are extremely sensitive to fluorine and silicon elements. The migration of silicon elements in the release agent will cause the product to short-circuit or open-circuit failure, so it will bring certain risks to processing and manufacturing. However, the processing and manufacturing process of electronic products still requires a suitable protective film for processing, so it is necessary to develop a release agent that does not contain silicon and fluorine elements for processing.

[0004] At present, common non-silicone release agents include long-chain alkane release agents and acrylic resin release agents, both of which are free of silicon and fluorine and can meet specific release requirements. Long-chain alkane non-silicone release agents are generally composed of two parts, including a polymer main chain and a long-chain alkane side chain. The non-polar long-chain alkane side chain is connected to the polymer through a certain bridging group and a reactive functional group on the polymer end group or side group. The polar group of the polymer provides a certain mechanical strength and adhesion, and the long-chain alkane provides a non-polar segment to ensure the release performance of the non-silicone release agent. In the currently disclosed release agent patents, the polymer main chain generally uses long-chain polymers containing hydroxyl or amino groups such as polyvinyl alcohol or polyethyleneimine, and the non-polar bridging group uses long-chain alkanes with active functional groups such as long-chain isocyanates or long-chain isothiocyanates. Its synthesis is relatively simple, and the product is a solid powder, which is convenient for transportation and use. The release force is stable at room temperature, but its temperature resistance is poor. When used at temperatures above 60°C, the release force increases seriously, and the adhesion is poor, and the residual adhesion rate is low. The acrylic resin release agent has good heat resistance and weather resistance due to its cross-linked structure, and has strong adhesion, but due to too many polar groups, the release performance is poor, which seriously damages the product. Summary of the invention

[0005] In view of this, the present invention proposes a cross-linked end-side long carbon chain polyurethane non-silicon release agent polymer, release agent and preparation method thereof, aiming to provide more cross-linking sites by using terminal hydroxyl polybutadiene containing unsaturated carbon-carbon double bonds, thereby ensuring the weather resistance and temperature resistance of the release agent, and at the same time using long-chain and short-chain alkane chain extenders to provide non-polar segments in the side chain to achieve good release performance of the release agent. The obtained non-silicon release agent has excellent thermal stability and release performance, simple preparation process, easy use, and the coated release film coating has good adhesion to the base layer.

[0006] The technical solution of the present invention is achieved as follows: The present invention provides a cross-linked end-side long carbon chain polyurethane non-silicone release agent polymer, the polymer having a structure of molecular formula I:

[0007]

[0008] Wherein -R1- is: -C2H4-, -C3H6-, -C4H8-, CH3CH(CH2-)2, CH3(CH2)9CH2COOCH2(CH-)CH2-, CH3(CH2) 11 CH2COOCH2(CH-)CH2-, CH3(CH2)7CH=CH(CH2)6CH2COOCH2(CH-)CH2-, CH3(CH2) 15 CH2COOCH2(CH-)CH2-, CH3(CH2)3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CH(CH2)2CH2COOCH2(CH-)CH2-, CH3(CH2) 16 A type of CH2N(CH2CH2-)2.

[0009] Wherein -R2- is: a benzyl group connected to two substitution positions on the benzene ring, a diphenylmethane group substituted at the 4th and 4'th positions, a hexyl group substituted at the 1st and 6th positions, One of the dicyclohexylmethane substituted at the 4-position and the 4'-position.

[0010] In a second aspect, the present invention provides a method for preparing a cross-linked end-side long carbon chain polyurethane non-silicone release agent polymer, the method comprising the following steps:

[0011] Step 1: adding diisocyanate dropwise to a hydroxy-terminated polybutadiene solution, and stirring at 20 to 120° C. for 0.5 to 24 hours under the action of a catalyst to obtain a polyurethane prepolymer solution;

[0012] Step 2, adding the alkane chain extender dropwise to the polyurethane prepolymer solution, stirring at 20 to 120° C. for 0.5 to 28 hours, to obtain a non-silicone release agent with a long-chain alkane chain extension;

[0013] Step 3: Dry and crush the non-silicon release agent obtained by the long-chain alkane extension in step 2 to obtain a polymer powder.

[0014] In some embodiments, the hydroxyl-terminated polybutadiene solution is obtained by mixing hydroxyl-terminated polybutadiene with a solvent, and the solvent is one or a combination of toluene and ethyl acetate.

[0015] In some embodiments, the preparation method of the hydroxyl-terminated polybutadiene solution includes: drying the hydroxyl-terminated polybutadiene at 70-150° C. and 0.01-100 kPa for 0.5-4 h, then adding a solvent, stirring and heating it to 20-120° C. to obtain a hydroxyl-terminated polybutadiene solution.

[0016] In some embodiments, the diisocyanate is a combination of one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate.

[0017] In some embodiments, the molecular weight of the hydroxy-terminated polybutadiene is 500 to 10,000.

[0018] In some embodiments, the catalyst is a combination of one or more of dibutyltin dilaurate, stannous octoate, and triethanolamine.

[0019] In some embodiments, the alkane chain extender is a combination of one or more of 1,4-butanediol, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, lauric acid monoglyceride, myristic acid monoglyceride, oleic acid monoglyceride, stearic acid monoglyceride, arachidic acid monoglyceride, and 2,2'-(octadecylimino)diethanol.

[0020] In some embodiments, the alkane chain extender in step 2 is dried before being added, and the drying method comprises: drying the alkane chain extender at 70-150° C. and 0.01-100 kPa for 0.5-4 h.

[0021] In some embodiments, the drying step described in step three includes: drying the long-chain alkane-extended non-silicon release agent obtained in step two at 20-80° C. and 0.01-100 kPa for 24-96 hours, cooling to -20-10° C. and drying at 0.01-100 kPa a for 12-72 hours.

[0022] In a third aspect, the present invention further provides a cross-linked end-side long carbon chain polyurethane non-silicon release agent, which is obtained by cross-linking and curing the aforementioned cross-linked end-side long carbon chain polyurethane non-silicon release agent polymer with a multifunctional vinyl monomer, and the cross-linked end-side long carbon chain polyurethane non-silicon release agent has a structure of molecular formula II:

[0023]

[0024] In a fourth aspect, the present invention further provides a method for preparing a cross-linked end-side long carbon chain polyurethane non-silicon release agent, which comprises the following steps:

[0025] The powder of the cross-linked end-side long carbon chain polyurethane non-silicone release agent polymer is mixed with toluene, a multifunctional vinyl monomer and a thermal initiator, and then stirred and dissolved at 10 to 50° C. to obtain a non-silicone release agent.

[0026] In some embodiments, the multifunctional vinyl monomer is a combination of one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and pentaerythritol diacrylate monostearate.

[0027] In some embodiments, the initiator is a combination of one or more of dibenzoyl oxide, azobisisobutyronitrile, and azobisisoheptylonitrile.

[0028] In a second aspect, the present invention also protects a non-silicon release agent of a cross-linked end-side long carbon chain polyurethane, which is prepared by the above-mentioned preparation method.

[0029] In some embodiments, the mass proportions of each component are: 80-100 parts of terminal hydroxyl polybutadiene, 10-20 parts of diisocyanate, 10-20 parts of alkane chain extender, 0.1-0.5 parts of catalyst, 500-1000 parts of solvent, 5-10 parts of thermal initiator, and 10-30 parts of multifunctional vinyl monomer.

[0030] In some embodiments, the reaction formula of the release agent is as follows:

[0031]

[0032] The cross-linked end-side long carbon chain polyurethane non-silicon release agent of the present invention has the following beneficial effects compared with the prior art:

[0033] The non-silicon release agent of the present invention is different from various non-silicon release agents disclosed. By adopting terminal hydroxyl polybutadiene containing unsaturated carbon chains, the acid resistance and temperature resistance of the release agent are improved, and more cross-linking sites are provided. At the same time, an alkane chain extender is adopted to provide non-polar chain segments in the side chains to ensure good release performance of the release agent.

[0034] The reaction process of the present invention is relatively simple, and the finished release agent polymer is a solid powder, which is convenient for transportation and use. Compared with most existing long-chain alkane non-silicon release agents, the carbon-carbon double bonds contained in the chain can provide better curing performance, so that it has better temperature resistance and more stable release performance, and the coated release film coating will have better adhesion to the base layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0036] Figure 1 FT-IR spectrum of the non-silicon release agent prepared in Example 3 of the raw material;

[0037] Figure 2 This is a schematic diagram of the air atmosphere thermogravimetric analysis of the non-silicone release film prepared in Example 2;

[0038] Figure 3 Schematic diagram of thermogravimetric analysis of the non-silicon release film prepared in Example 2 under nitrogen atmosphere. DETAILED DESCRIPTION

[0039] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the embodiments of the present invention belong. If the definitions set forth in this section are contrary to or otherwise inconsistent with the definitions set forth in the patents, patent applications, published patent applications, and other publications incorporated herein by reference, the definitions listed in this section take precedence over the definitions incorporated herein by reference.

[0041] Unless otherwise specified, the methods used in the following examples are all conventional methods. Unless otherwise specified, the materials, reagents and instruments used are all conventional materials, reagents and instruments in the art, and can be obtained by those skilled in the art through commercial channels.

[0042] When an amount, concentration or other value or parameter is expressed as a range, a preferred range or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including the range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range. In the present specification and claims, range definitions can be combined and / or interchanged, and if not otherwise stated, these ranges include all subranges contained therein.

[0043] Example 1

[0044] A cross-linked end-side long carbon chain polyurethane non-silicone release agent, the components of which are as follows by weight: 80 parts of terminal hydroxyl polybutadiene, 10 parts of diisocyanate, 10 parts of long-chain and short-chain alkane chain extenders, 0.1 parts of catalysts, 500 parts of solvents, 5 parts of thermal initiators, and 10 parts of multifunctional vinyl monomers.

[0045] The molecular weight of the terminal hydroxyl polybutadiene is 500Da, the diisocyanate is toluene diisocyanate, the alkane chain extender is 1,4-butanediol and lauric acid monoglyceride, the catalyst is dibutyltin dilaurate, the thermal initiator is dibenzoyl peroxide, the multifunctional vinyl monomer is trimethylolpropane triacrylate, and the solvent is ethyl acetate.

[0046] Preparation of polyurethane long-chain non-silicone release agent:

[0047] The hydroxyl-terminated polybutadiene was dried at 70°C and 0.01 kPa for 4 hours, and then a solvent was added, which was continuously stirred and heated to 20°C to obtain a hydroxyl-terminated polybutadiene solution;

[0048] The diisocyanate is added dropwise to the prepared hydroxy-terminated polybutadiene solution, and a certain amount of catalyst is added. After the addition is completed, the mixture is stirred at a constant temperature for 24 hours to obtain a polyurethane prepolymer solution.

[0049] The alkane chain extender was dried at 70°C and 0.01 kPa for 4 hours, and then added dropwise to the prepared polyurethane prepolymer solution. After the addition was completed, the solution was stirred at 20°C for 28 hours to obtain a non-silicone release agent with a long-chain alkane chain extension;

[0050] After the reaction is completed, the mixture is dried at 20°C and 0.01 kPa for 96 h, cooled to -20°C, dried at 0.01 kPa for 12 h, and then fully ground to obtain a polymer powder;

[0051] The prepared polymer powder was added into toluene, and a multifunctional vinyl monomer and a thermal initiator were added, and the mixture was stirred and dissolved at 10° C. to obtain a release agent coating solution.

[0052] Example 2

[0053] A cross-linked end-side long carbon chain polyurethane non-silicone release agent, the components of which are as follows by weight: 100 parts of terminal hydroxyl polybutadiene, 20 parts of diisocyanate, 20 parts of long-chain and short-chain alkane chain extenders, 0.5 parts of catalyst, 1000 parts of solvent, 10 parts of thermal initiator, and 30 parts of multifunctional vinyl monomer.

[0054] The molecular weight of the terminal hydroxyl polybutadiene is 10000Da, the diisocyanate is 4,4'-diphenylmethane diisocyanate, the alkane chain extender is ethylene glycol and myristic acid monoglyceride, the catalyst is triethanolamine, the thermal initiator is azobisisobutyronitrile, the multifunctional vinyl monomer is pentaerythritol tetraacrylate, and the solvent is ethyl acetate.

[0055] Preparation of polyurethane long-chain non-silicone release agent:

[0056] The hydroxyl-terminated polybutadiene was dried at 150° C. and 100 kPa for 4 h, and then a solvent was added, which was continuously stirred and heated to 120° C. to obtain a hydroxyl-terminated polybutadiene solution;

[0057] The diisocyanate is added dropwise to the prepared hydroxy-terminated polybutadiene solution, and a certain amount of catalyst is added. After the addition is completed, the mixture is stirred at a constant temperature for 0.5 h to obtain a polyurethane prepolymer solution.

[0058] The alkane chain extender is dried at 150° C. and 100 kPa for 4 hours, and then added dropwise to the prepared polyurethane prepolymer solution. After the addition is completed, the solution is stirred at 120° C. for 0.5 hours to obtain a non-silicone release agent with a long-chain alkane chain extension;

[0059] After the reaction is completed, the mixture is dried at 80°C and 0.01 kPa for 24 h, cooled to -20°C, dried at 100 kPa for 72 h, and then fully ground to obtain a polymer powder;

[0060] The prepared polymer powder is added into toluene, and a multifunctional vinyl monomer and a thermal initiator are added thereto, and the mixture is stirred and dissolved at 50° C. to obtain a release agent coating solution.

[0061] Example 3

[0062] A cross-linked end-side long carbon chain polyurethane non-silicone release agent, the components of which are as follows by weight: 100 parts of terminal hydroxyl polybutadiene, 15 parts of diisocyanate, 15 parts of alkane chain extender, 0.2 parts of catalyst, 500 parts of solvent, 5 parts of thermal initiator, and 10 parts of multifunctional vinyl monomer.

[0063] The molecular weight of the terminal hydroxyl polybutadiene is 2000Da, the diisocyanate is hexamethylene diisocyanate, the alkane chain extender is stearic acid monoglyceride, the catalyst is dibutyltin dilaurate, the thermal initiator is azobisisoheptanenitrile, the multifunctional vinyl monomer is pentaerythritol triacrylate, and the solvent is toluene.

[0064] Preparation of polyurethane long-chain non-silicone release agent:

[0065] The hydroxyl-terminated polybutadiene was dried at 140° C. and 0.01 kPa for 0.5 h, and then a solvent was added, which was continuously stirred and heated to 80° C. to obtain a hydroxyl-terminated polybutadiene solution;

[0066] The diisocyanate is added dropwise to the prepared hydroxy-terminated polybutadiene solution, and a certain amount of catalyst is added. After the addition is completed, the mixture is stirred at a constant temperature for 3 hours to obtain a polyurethane prepolymer solution.

[0067] The alkane chain extender was dried at 140° C. and 0.01 kPa for 0.5 h, and then added dropwise to the prepared polyurethane prepolymer solution. After the addition was completed, the solution was stirred at 80° C. for 3 h to obtain a non-silicone release agent with a long-chain alkane chain extension;

[0068] After the reaction is completed, the mixture is dried at 50°C and 100 kPa for 96 h, cooled to 10°C, dried at 0.01 kPa for 72 h, and then fully ground to obtain a polymer powder;

[0069] The prepared polymer powder was added into toluene, and a multifunctional vinyl monomer and a thermal initiator were added, and the mixture was stirred and dissolved at 10° C. to obtain a release agent coating solution.

[0070] Example 4

[0071] A cross-linked end-side long carbon chain polyurethane non-silicone release agent, the components of which are as follows by weight: 100 parts of terminal hydroxyl polybutadiene, 13 parts of diisocyanate, 17 parts of alkane chain extender, 0.2 parts of catalyst, 500 parts of solvent, 5 parts of thermal initiator, and 10 parts of multifunctional vinyl monomer.

[0072] Among them: the molecular weight of the terminal hydroxyl polybutadiene is 2000Da, the diisocyanate is isophorone diisocyanate, the long-chain and short-chain alkane chain extenders are 2-methyl-1,3-propanediol and monooleyl glycerol, the catalyst is stannous octoate, the thermal initiator is dibenzoyl peroxide, the multifunctional vinyl monomer is pentaerythritol tetraacrylate, and the solvent is ethyl acetate.

[0073] Preparation of polyurethane long-chain non-silicone release agent:

[0074] The hydroxyl-terminated polybutadiene was dried at 110° C. and 0.01 kPa for 2 h, and then a solvent was added, which was continuously stirred and heated to 80° C. to obtain a hydroxyl-terminated polybutadiene solution;

[0075] The diisocyanate is added dropwise to the prepared hydroxy-terminated polybutadiene solution, and a certain amount of catalyst is added. After the addition is completed, the mixture is stirred at a constant temperature for 3 hours to obtain a polyurethane prepolymer solution.

[0076] The alkane chain extender was dried at 110° C. and 0.01 kPa for 2 h, and then added dropwise to the prepared polyurethane prepolymer solution. After the addition was completed, the solution was stirred at 80° C. for 3 h to obtain a non-silicone release agent with a long-chain alkane chain extension.

[0077] After the reaction is completed, the mixture is dried at 50°C and 0.01 kPa for 96 h, cooled to -20°C, dried at 0.01 kPa for 72 h, and then fully ground to obtain a polymer powder;

[0078] The prepared polymer powder is added into toluene, and a multifunctional vinyl monomer and a thermal initiator are added thereto, and the mixture is stirred and dissolved at 30° C. to obtain a release agent coating solution.

[0079] Example 5

[0080] A cross-linked end-side long carbon chain polyurethane non-silicone release agent, the components of which are as follows by weight: 90 parts of terminal hydroxyl polybutadiene, 15 parts of diisocyanate, 15 parts of alkane chain extender, 0.2 parts of catalyst, 500 parts of solvent, 8 parts of thermal initiator and 15 parts of multifunctional vinyl monomer.

[0081] The molecular weight of the terminal hydroxyl polybutadiene is 4000Da, the diisocyanate is dicyclohexylmethane-4,4'-diisocyanate, the long-chain and short-chain alkane chain extenders are propylene glycol and arachidic acid monoglyceride, the catalyst is dibutyltin dilaurate, the thermal initiator is dibenzoyl peroxide, the multifunctional vinyl monomer is pentaerythritol tetraacrylate, and the solvent is ethyl acetate.

[0082] Preparation of polyurethane long-chain non-silicone release agent:

[0083] The hydroxyl-terminated polybutadiene was dried at 110° C. and 0.01 kPa for 3 h, and then a solvent was added, which was continuously stirred and heated to 80° C. to obtain a hydroxyl-terminated polybutadiene solution;

[0084] The diisocyanate is added dropwise to the prepared hydroxy-terminated polybutadiene solution, and a certain amount of catalyst is added. After the addition is completed, the mixture is stirred at a constant temperature for 2 hours to obtain a polyurethane prepolymer solution.

[0085] The alkane chain extender was dried at 110° C. and 0.01 kPa for 3 h, and then added dropwise to the prepared polyurethane prepolymer solution. After the addition was completed, the solution was stirred at 80° C. for 2 h to obtain a non-silicone release agent with a long-chain alkane chain extension.

[0086] After the reaction is completed, the mixture is dried at 50°C and 0.01 kPa for 24 h, cooled to -20°C, dried at 0.01 kPa for 72 h, and then fully ground to obtain a polymer powder;

[0087] The prepared polymer powder is added into toluene, and a multifunctional vinyl monomer and a thermal initiator are added thereto, and the mixture is stirred and dissolved at 30° C. to obtain a release agent coating solution.

[0088] Example 6

[0089] A cross-linked end-side long carbon chain polyurethane non-silicone release agent, the components of which are as follows by weight: 100 parts of terminal hydroxyl polybutadiene, 15 parts of diisocyanate, 15 parts of alkane chain extender, 0.2 parts of catalyst, 500 parts of solvent, 10 parts of thermal initiator and 15 parts of multifunctional vinyl monomer.

[0090] The molecular weight of the terminal hydroxyl polybutadiene is 4000Da, the diisocyanate is toluene diisocyanate, the long-chain and short-chain alkane chain extenders are 2,2'-(octadecyl imino) diethanol, the catalyst is dibutyltin dilaurate, the thermal initiator is dibenzoyl peroxide, the multifunctional vinyl monomer is pentaerythritol diacrylate monostearate, and the solvent is ethyl acetate.

[0091] Preparation of polyurethane long-chain non-silicone release agent:

[0092] The hydroxyl-terminated polybutadiene was dried at 110° C. and 0.01 kPa for 2 h, and then a solvent was added, which was continuously stirred and heated to 70° C. to obtain a hydroxyl-terminated polybutadiene solution;

[0093] The diisocyanate is added dropwise to the prepared hydroxy-terminated polybutadiene solution, and a certain amount of catalyst is added. After the addition is completed, the mixture is stirred at a constant temperature for 2 hours to obtain a polyurethane prepolymer solution.

[0094] The alkane chain extender was dried at 110° C. and 0.01 kPa for 2 h, and then added dropwise to the prepared polyurethane prepolymer solution. After the addition was completed, the solution was stirred at 70° C. for 2 h to obtain a non-silicone release agent with a long-chain alkane chain extension.

[0095] After the reaction is completed, the mixture is dried at 50°C and 0.01 kPa for 24 h, cooled to -20°C, dried at 0.01 kPa for 72 h, and then fully ground to obtain a polymer powder;

[0096] The prepared polymer powder is added into toluene, and a multifunctional vinyl monomer and a thermal initiator are added thereto, and the mixture is stirred and dissolved at 30° C. to obtain a release agent coating solution.

[0097] Comparative Example 1

[0098] A cross-linked end-side long carbon chain polyurethane non-silicone release agent, the components of which are as follows by weight: 100 parts of terminal hydroxyl polybutadiene, 15 parts of diisocyanate, 15 parts of chain extender, 0.2 parts of catalyst, 500 parts of solvent, 10 parts of thermal initiator and 15 parts of multifunctional vinyl monomer.

[0099] The molecular weight of the terminal hydroxyl polybutadiene is 2000Da, the diisocyanate is toluene diisocyanate, the chain extender is 1,4-butanediol, the catalyst is dibutyltin dilaurate, the thermal initiator is dibenzoyl peroxide, the multifunctional vinyl monomer is pentaerythritol tetraacrylate, and the solvent is ethyl acetate.

[0100] Preparation of polyurethane long-chain non-silicone release agent:

[0101] The hydroxyl-terminated polybutadiene was dried at 110° C. and 0.01 kPa for 2 h, and then a solvent was added, which was continuously stirred and heated to 70° C. to obtain a hydroxyl-terminated polybutadiene solution;

[0102] The diisocyanate is added dropwise to the prepared hydroxy-terminated polybutadiene solution, and a certain amount of catalyst is added. After the addition is completed, the mixture is stirred at a constant temperature for 2 hours to obtain a polyurethane prepolymer solution.

[0103] The chain extender was dried at 110° C. and 0.01 kPa for 2 h, and then added dropwise to the prepared polyurethane prepolymer solution. After the addition was completed, the solution was stirred at 70° C. for 2 h to obtain a non-silicone release agent with a long-chain alkane chain extension.

[0104] After the reaction was completed, the polymer liquid was obtained after drying at 50°C and 0.01 kPa for 24 h;

[0105] The prepared polymer liquid was added into toluene, and a multifunctional vinyl monomer and a thermal initiator were added, and the mixture was stirred and dissolved at 30° C. to obtain a release agent coating solution.

[0106] Comparative Example 2

[0107] A cross-linked end-side long carbon chain polyurethane non-silicone release agent, the components of which are as follows by weight: 100 parts of terminal hydroxyl polybutadiene, 15 parts of diisocyanate, 15 parts of alkane chain extender, 0.2 parts of catalyst and 500 parts of solvent.

[0108] The molecular weight of the terminal hydroxyl polymer is 2000Da, the diisocyanate is toluene diisocyanate, the alkane chain extender is 2,2'-(octadecyl imino) diethanol, the catalyst is dibutyltin dilaurate, and the solvent is ethyl acetate.

[0109] Preparation of polyurethane long-chain non-silicone release agent:

[0110] The hydroxyl-terminated polybutadiene was dried at 110° C. and 0.01 kPa for 2 h, and then a solvent was added, which was continuously stirred and heated to 80° C. to obtain a hydroxyl-terminated polybutadiene solution;

[0111] The diisocyanate is added dropwise to the prepared hydroxy-terminated polybutadiene solution, and a certain amount of catalyst is added. After the addition is completed, the mixture is stirred at a constant temperature for 2 hours to obtain a polyurethane prepolymer solution.

[0112] The alkane chain extender was dried at 110° C. and 0.01 kPa for 2 h, and then added dropwise to the prepared polyurethane prepolymer solution. After the addition was completed, the solution was stirred at 70° C. for 2 h to obtain a non-silicone release agent with a long-chain alkane chain extension.

[0113] After the reaction is completed, the mixture is dried at 50°C and 0.01 kPa for 24 h, cooled to -20°C, dried at 0.01 kPa for 72 h, and then fully ground to obtain a polymer powder;

[0114] The prepared polymer powder was added into toluene and dissolved by stirring at 30° C. to obtain a release agent coating solution.

[0115] The release agent coating solutions prepared in the above examples and comparative examples were tested respectively, and the specific test items and test methods are as follows:

[0116] (1) 20min rapid release force test, room temperature required to be 23℃, humidity required to be 50%~60%, test tape used is Nitto 31B, after the test tape is applied, use 2kg standard roller, roll four times at a speed of 600mm / min, leave at room temperature for 20min before testing, the speed of the tensile machine during the test is 300mm / min.

[0117] (2) 24h aging release force test, room temperature required to be 23℃, humidity required to be 50%~60%, test tape used is Nitto 31B, after the test tape is applied, use 2kg standard roller, roll it four times at a speed of 600mm / min, leave it at room temperature for 24h before testing, the speed of the tensile machine during the test is 300mm / min.

[0118] (3) Residual adhesion test: The initial sample preparation method is the same as the aging test preparation method. Take a few KJ-6001A test steel plates, and transfer the Nitto 31B tape attached to the release film taken out of the drying oven to the test steel plate. Use a 2kg roller to press 4 times and then let it stand for 20 minutes before testing. The test result is A1. Take the standard Nitto 31B tape and stick it on the steel plate. Press it 4 times in the same way. The test peel force is taken as the standard value B1. A1 / B1*100% is the residual adhesion rate of the sample.

[0119] (4) High temperature aging test: the coated release film was placed in a 100°C forced air drying oven for 12 hours and then taken out and placed at room temperature for 1 hour. The test process was the same as the sample preparation method described above and the test was performed.

[0120] The specific test results are shown in the following table:

[0121]

[0122] At the same time, the release agent prepared in the above Example 3 was analyzed by Fourier infrared spectroscopy, and the following Figure 1 As shown in the results, it can be seen that the target product of formula I of the present invention can be obtained by adopting the preparation method of the present invention. Figure 2 and Figure 3 They are respectively schematic diagrams of thermogravimetric analysis of the release agent prepared in Example 2 after film formation in air atmosphere and nitrogen atmosphere, wherein the black line portion is the TG curve and the red line portion is the DTG curve.

[0123] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A cross-linked end-side long carbon chain polyurethane non-silicon release agent, characterized in that: The cross-linked end-side long carbon chain polyurethane non-silicone release agent is obtained by cross-linking and curing a polymer with a multifunctional vinyl monomer, and the polymer has a structure of molecular formula I: Formula I Wherein: -R1- is: -C2H4-, -C3H6-, -C4H8-, CH3CH(CH2-)2, CH3(CH2)9CH2COOCH2(CH-)CH2-, CH3(CH2) 11 CH2COOCH2 (CH-) CH2-, CH3 (CH2) 7 CH=CH (CH2) 6CH2COOCH2 (CH-) CH2-, CH3 (CH2) 15 CH2COOCH2 (CH-) CH2-, CH3 (CH2) 3CH2CH = CHCH2CH = CHCH2CH = CHCH2CH = CH (CH2) 2CH2COOCH2 (CH-) CH2-, CH3 (CH2) 16 A type of CH2N(CH2CH2-)2; -R2- is: a benzyl group connected to two substitution positions on the benzene ring, a diphenylmethane group substituted at the 4th and 4'th positions, a hexyl group substituted at the 1st and 6th positions, , one of dicyclohexylmethane substituted at the 4-position and the 4'-position; The preparation method of the cross-linked end-side long carbon chain polyurethane non-silicon release agent comprises: Step 1: adding diisocyanate dropwise to a hydroxy-terminated polybutadiene solution, and stirring at 20 to 120° C. for 0.5 to 24 hours under the action of a catalyst to obtain a polyurethane prepolymer solution; Step 2: adding the alkane chain extender dropwise to the polyurethane prepolymer solution, and stirring at 20-120° C. for 0.5-28 hours to obtain a non-silicone release agent with a long-chain alkane chain extension; Step 3, drying and crushing the non-silicon release agent obtained by the long-chain alkane chain extension in step 2 to obtain a polymer powder; Step 4: Mix the polymer powder with toluene, multifunctional vinyl monomer and thermal initiator, and stir and dissolve at 10-50° C. to obtain a non-silicone release agent.

2. The cross-linked end-side long carbon chain polyurethane non-silicon release agent according to claim 1, characterized in that: The hydroxyl-terminated polybutadiene solution is obtained by mixing hydroxyl-terminated polybutadiene with a solvent, and the solvent is one or a combination of toluene and ethyl acetate.

3. The cross-linked end-side long carbon chain polyurethane non-silicon release agent according to claim 1, characterized in that: The diisocyanate is a combination of one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate.

4. The cross-linked end-side long carbon chain polyurethane non-silicon release agent according to claim 1, characterized in that: The molecular weight of the hydroxy-terminated polybutadiene is 500-10000.

5. The cross-linked end-side long carbon chain polyurethane non-silicon release agent according to claim 1, characterized in that: The catalyst is a combination of one or more of dibutyltin dilaurate, stannous octoate and triethanolamine.

6. The method for preparing a cross-linked end-side long carbon chain polyurethane non-silicon release agent polymer according to claim 1, characterized in that: The drying step described in step three includes: drying the non-silicon release agent obtained in step two at 20-80°C and 0.01-100 kPa for 24-96 hours, cooling to -20-10°C, and drying at 0.01-100 kPa for 12-72 hours.

7. The cross-linked end-side long carbon chain polyurethane non-silicon release agent according to claim 1, characterized in that: The multifunctional vinyl monomer is a combination of one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate monostearate.

8. The cross-linked end-side long carbon chain polyurethane non-silicon release agent according to claim 1, characterized in that: The thermal initiator is a combination of one or more of dibenzoyl oxide, azobisisobutyronitrile and azobisisoheptylnitrile.

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