Background
Release agents are a general term for a class of materials used between two materials (media) to prevent adhesion therebetween or to control the adhesion strength of both materials to a desired value, and are widely used. The release agent is divided into an inorganic type and an organic type from the material aspect; the use modes are divided into an internal lubrication type and an external isolation type. Release agents commonly used in the pressure sensitive adhesive article industry are primarily organic release agents that function primarily by external insulation, such as surface coating.
The organic mold release mainly comprises an organic silicon mold release, an organic fluorine mold release and other organic mold release; in the pressure-sensitive adhesive product industry, the application range of the organic silicon release agent is the widest, the using amount is the largest, and the using effect is the best.
The organic silicon release agent can be divided into three categories of solvent type, emulsion type and solvent-free type. The solvent type and emulsion type are the most widely used in China, and the solvent-free type is more and more applied in certain fields. The solvent type and the solvent-free type are mainly used for films, and the emulsion type is mainly used for paper.
The solvent-type and solvent-free organic silicon release agents mainly adopt addition, adopt platinum as a catalyst, and realize heat curing at the temperature of over 140 ℃ for 25 seconds. It is entirely feasible to carry out the coating process on a substrate that can withstand such process conditions. However, if the substrate is a Polyethylene (PE) film, such process conditions can deform or even melt the Polyethylene (PE) film. Therefore, solvent-based and solvent-free silicone release agents are not suitable for PE films. Thus, considering both the excellent release properties of silicone release agents and the reduction of the coating crosslinking conditions of release agents to levels that can be tolerated by PE films, it is desirable to modify silicone release agents from the molecular structure, i.e., to both retain polysiloxane segments in the molecular structure and to introduce groups that can crosslink below 110 ℃, such as amino, hydroxyl, carboxyl, and the like.
There are several methods for preparing the modified organosilicon release agent, and the method is selected according to different purposes. The modified object is used on a PE film and is a release agent for rubber type pressure-sensitive adhesive, and the release agent is easy to unwind and controlled within a proper unwinding force range so as to facilitate the coating production, slitting and smooth use of the protective film. It is also considered that the silicone anti-adhesive coating reduces the adhesion of the pressure-sensitive adhesive to different degrees, and the main reason for this is the transfer of the small molecule silicone which is not crosslinked. Therefore, it is considered that a multifunctional siloxane is introduced into an acrylate molecule, then the multifunctional siloxane acrylate is copolymerized with other (hydroxyl) acrylate to obtain an acrylate modified silicone release agent, and then a release agent coating layer with a release effect can be formed on the PE film by adopting a proper crosslinking mode, coating, drying and the like.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a release agent for a rubber type PE protective film, which has the technical scheme as follows:
the preparation process of the release agent for the rubber type PE protective film is divided into two steps, wherein the first step is the synthesis of a multifunctional siloxane acrylate monomer; and the second step is to copolymerize the monomer obtained in the first step with other acrylates and other vinyl monomers to obtain the mold release agent.
(1) Preparation of the polyfunctional allyloxy siloxane (A): the multifunctional allyloxy siloxane (A) is obtained by reacting allyloxy silane, alkyl alkoxy silane, water and catalyst under the action of a polymerization inhibitor. The reaction temperature is controlled between 35 ℃ and 95 ℃.
(2) Preparing a release agent for the rubber type PE protective film: copolymerizing A, hydroxyl acrylate, (methyl) acrylate and styrene in an organic solvent under the action of an initiator to obtain the release agent for the rubber type PE protective film.
On the basis of the above principle technical scheme, the invention also makes the following improvements.
Further, the step (1) of hydrolysis reaction among molecules of the allyloxysilane, the alkylalkoxysilane, water and the acidic catalyst is carried out under the action of a polymerization inhibitor, the reaction temperature is controlled to be 35-95 ℃, and reaction products with low boiling points are gradually evaporated in the reaction process.
The formulation is designed with the desired degree of siloxane functionality. The relative proportions of the main reactants and the catalyst are determined, the volatile component produced by the reaction is determined according to the reactants, the reaction temperature is determined, and the temperature and time for completing the evaporation (reaction production) of the volatile component are determined.
The sequence of addition, the method of addition, directly affects the orientation of the hydrolysis reaction products. The invention is characterized in that: firstly, adding the allyloxysilane into a reaction kettle, then adding the polymerization inhibitor, stirring and dissolving, and then adding the alkyl alkoxy silane. The catalyst is firstly dissolved in water and added in a manner of reaction and dropwise addition.
The extent of reaction progress was determined by the amount of the collected distilled low-boiling reaction product.
Further, the allyloxysilane may be: one or more of methyl allyloxypropyl methyl dimethoxysilane, methyl allyloxypropyl ethyl dimethoxysilane and methyl allyloxypropyl trimethoxysilane;
further, the alkylalkoxysilane may be: one or more of methyl triethoxysilane, methyl trimethoxysilane, ethyl triethoxysilane, and ethyl trimethoxysilane;
further, the water is distilled water;
further, the acidic catalyst may be: one of trifluoromethanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid and hydrochloric acid;
further, the polymerization inhibitor is one of hydroquinone, p-benzoquinone and p-tert-butyl catechol;
furthermore, the adding amount of the water (including the water brought by other raw materials) is determined by the hydrolysis rate of alkoxy groups in all silane molecules in the reaction system, and the hydrolysis rate is controlled within 80 percent;
further, the catalyst is firstly dissolved in water, and the dropwise addition is controlled to be completed within 5-15 minutes in a mode of gradually dropwise adding in the reaction process;
further, reaction products with low boiling points are gradually evaporated in the reaction process, in the invention, the products refer to alcohols, such as ethanol or methanol, and different final evaporation temperatures exist for different alcohols;
further, in the step (2), the multifunctional allylacyloxy siloxane obtained by the reaction in the step (1) is copolymerized with (methyl) acrylate, styrene and the like in an organic solvent under the action of an initiator to obtain an acrylate modified organic silicon release agent;
further, said multifunctional allyloxy siloxane, in fact, still contains a proportion of alkoxy groups, which still have the property of being hydrolytically condensable;
further, the (meth) acrylate: can be two or more of methyl methacrylate, methyl acrylate, ethyl methacrylate, methyl acrylate and butyl acrylate;
further, the organic solvent is one or a mixture of two or three of ethyl acetate, butyl acetate and toluene;
further, the initiator is one of Benzoyl Peroxide (BPO), Azobisisobutyronitrile (AIBN);
further, the rubber type release agent for the PE protective film is obtained through copolymerization, the main mass of the release agent is a copolymer of acrylic esters and a small amount of other vinyl-containing monomers, the organic silicon part is the smaller mass, the organic silicon part still has a release effect, and other polymers play a synergistic effect. The invention thus still refers to the product as: acrylate modified silicone release agents;
further, the release agent for the rubber type PE protective film still retains the acidic catalyst in the step (1), which is beneficial to the wet crosslinking process of the release coating and is beneficial to the improvement of the strength of the release coating;
further, in an application test, the release agent for the rubber type PE protective film needs to be diluted to a required solid content by a solvent, isocyanate is used as a cross-linking agent, then the release agent is coated on a PE film, and a release agent coating with a corresponding release effect can be formed after drying, curing and natural aging for a certain time, so that the release agent coating can be used for playing a proper release effect on the rubber type pressure sensitive adhesive; .
Detailed Description
The present invention will be described in more detail with reference to specific preferred embodiments, but the present invention is not limited to the following embodiments.
Example one
(1) Preparation of the polyfunctional allyloxy siloxane (A):
adding the following components in parts by weight into a four-neck flask provided with a heating device, a reflux condenser, a thermometer, a dropping funnel and a stirrer: 7.7 parts of methyl allyloxy propyl trimethoxy silane, 82.3 parts of methyl trimethoxy silane, 0.2 part of hydroquinone and 8.0 parts of distilled water, and a stirrer is started. 0.08 part of concentrated hydrochloric acid (C ═ 37% Wt) was dissolved in 2 parts of distilled water, and then transferred to a dropping funnel for use. At room temperature, liquid in the dropping funnel is dripped into the flask at a constant speed for 5 minutes, the temperature of the reaction materials naturally rises along with the dripping, the reflux is started at 68 ℃, the temperature of the reaction materials is reduced to 65 ℃ after the reflux is maintained for 30 minutes, the stirring is stopped, the reflux condenser is replaced by a distillation condenser pipe, and the light components generated by the reaction are prepared to be collected. After the components are ready, stirring and heating are restarted, the temperature of the reaction materials is continuously increased along with the continuous evaporation of the light components, when the temperature is increased to 95 ℃, no distillate exists, the distillation operation is stopped, and the components A are obtained by cooling and discharging.
(2) Preparing a release agent for the rubber type PE protective film:
a four-necked flask polymerization system equipped with a heating device, a reflux condenser, a thermometer, a dropping funnel and a stirrer was prepared, and 44 parts of ethyl acetate was charged into the flask.
The monomer and initiator solution are as follows by weight: the component A16 parts, the ethyl acrylate 7.4 parts, the methyl methacrylate 4.4 parts, the butyl acrylate 7.6 parts, the styrene 3.4 parts and the acrylic acid-2-hydroxypropyl ester 1.2 parts are mixed evenly, and the AIBN 0.6 part is dissolved in the mixed monomer.
Starting a stirrer, adding 10 parts of mixed monomer liquid into the flask, and starting heating; the remaining monomer mixture was transferred to the dropping funnel for further use.
When the temperature of the materials in the flask rises to about 77 ℃, the reflux starts to exist, after the reflux is maintained for 40 minutes, the rest monomer mixed solution is dripped into the flask at a constant speed for 1.5 hours, and the reaction materials are kept in a reflux state in the period. And after the monomer mixed solution is dropwise added, continuously maintaining the reflux state for 50 minutes, adding a solution of 0.1 part of AIBN and 16 parts of ethyl acetate into a dropping funnel, dropwise adding the solution into a flask within 10 minutes, continuously maintaining the reflux reaction for 2 hours, cooling and discharging to obtain the release agent for the rubber type PE protective film.
Example two
(1) Preparation of the polyfunctional allyloxy siloxane (A):
directly using component A obtained in example one
(2) Preparing a release agent for the rubber type PE protective film:
a four-necked flask polymerization reaction system equipped with a heating device, a reflux condenser, a thermometer, a dropping funnel and a stirrer was prepared, and 53.6 parts of ethyl acetate was charged into the flask.
The monomer and the initiator solution are as follows by weight: the component A17.8 parts, the ethyl acrylate 3.6 parts, the methyl methacrylate 2.2 parts, the butyl acrylate 3.8 parts, the styrene 1.7 parts and the acrylic acid-2-hydroxypropyl ester 1.3 parts are mixed evenly, and the AIBN 0.32 part is dissolved in the mixed monomer.
Starting a stirrer, adding 10.0 parts of mixed monomer liquid into the flask, and starting heating; the remaining monomer mixture was transferred to the dropping funnel for further use.
When the temperature of the materials in the flask rises to about 77 ℃, the reflux starts, after the reflux is maintained for 40 minutes, the rest monomer mixed solution is dropwise added into the flask at a constant speed for 1.5 hours, and the reaction materials are kept in a reflux state in the period. And after the dropwise addition of the monomer mixed solution is finished, continuously maintaining the reflux state for 50 minutes, adding a solution of 0.1 part of AIBN and 16 parts of ethyl acetate into a dropping funnel, dropwise adding the solution into a flask within 10 minutes, continuously maintaining the reflux reaction for 2 hours, cooling and discharging to obtain the release agent for the rubber type PE protective film.
EXAMPLE III
(1) Preparation of the polyfunctional allyloxy siloxane (A):
adding the following components in parts by weight into a four-neck flask provided with a heating device, a reflux condenser, a thermometer, a dropping funnel and a stirrer: 8.4 parts of methyl allyloxypropyltrimethoxysilane, 80.6 parts of methyl trimethoxysilane, 0.18 part of hydroquinone and 9.0 parts of distilled water, and a stirrer is started. 0.03 part of concentrated hydrochloric acid (C ═ 37% Wt) was dissolved in 2.0 parts of distilled water, and then transferred to a dropping funnel for use. At room temperature, dripping the liquid in the dropping funnel into the flask at a constant speed for 10 minutes, wherein along with the dripping, the temperature of the reaction material naturally rises, the reflux is started at 68 ℃, after the reflux is carried out for 60 minutes under the condition of heat preservation, the temperature of the reaction material is reduced to 65 ℃, the stirring is stopped, the reflux condenser is replaced by a distillation condenser pipe, and the light components generated by the reaction are prepared to be collected. And (3) restarting stirring and heating after the components are ready, continuously increasing the temperature of the reaction materials along with continuous evaporation of the light components, stopping distillation operation when the temperature is increased to 95 ℃ and no distillate exists, and cooling and discharging to obtain the component A.
(2) Preparing an acrylate modified organic silicon release agent:
a four-necked flask polymerization reaction system equipped with a heating device, a reflux condenser, a thermometer, a dropping funnel and a stirrer was prepared, and 54 parts of ethyl acetate was charged into the flask.
The monomer and initiator solution are as follows by weight: the component A17.9 parts, the ethyl acrylate 2.6 parts, the methyl methacrylate 2.3 parts, the butyl acrylate 3.1 parts, the styrene 2.6 parts and the acrylic acid-2-hydroxypropyl ester 1.5 parts are mixed evenly, and the AIBN 0.3 part is dissolved in the mixed monomer.
Starting a stirrer, adding 7.5 parts of mixed monomer liquid into the flask, and starting heating; the remaining monomer mixture was transferred to the dropping funnel for further use.
When the temperature of the materials in the flask rises to about 77 ℃, the reflux starts, after the reflux is maintained for 40 minutes, the rest monomer mixed solution is dropwise added into the flask at a constant speed for 2.0 hours, and the reaction materials are kept in a reflux state in the period. After the monomer mixed solution is dropwise added, continuously maintaining the reflux state for 45 minutes, and then adding AIBN: adding 0.05 part of AIBN and 8 parts of ethyl acetate into a dropping funnel, dropping into the flask within 5 minutes, and continuously maintaining reflux reaction for 1 hour; second supplement of AIBN: and (3) continuously keeping the reflux reaction for 1 hour in the same way as the first supplement of the same amount and the operation process, and cooling and discharging to obtain the release agent for the rubber type PE protective film.
Example four
(1) Preparation of the polyfunctional allyloxy siloxane (A):
adding the following components in parts by weight into a four-neck flask provided with a heating device, a reflux condenser, a thermometer, a dropping funnel and a stirrer: 9.1 parts of methyl allyl acyloxy propyl trimethoxy silane, 80.9 parts of methyl trimethoxy silane, 0.1 part of hydroquinone and 8.0 parts of distilled water, and a stirrer is started. 0.06 part of concentrated hydrochloric acid (C ═ 37% Wt) was dissolved in 2 parts of distilled water, and then transferred to a dropping funnel for use. At room temperature, liquid in the dropping funnel is dropped into the flask at a constant speed for 15 minutes, the temperature of the reaction materials can naturally rise along with the dropping, the reflux is started at 65 ℃, the temperature of the reaction materials is reduced to 65 ℃ after the reflux is carried out for 60 minutes under the condition of heat preservation, the stirring is stopped, the reflux condenser is replaced by a distillation condenser pipe, and the light components generated by the reaction are prepared to be collected. After the components are ready, stirring and heating are restarted, the temperature of the reaction materials is continuously increased along with the continuous evaporation of the light components, when the temperature is increased to 95 ℃, no distillate exists, the distillation operation is stopped, and the components A are obtained by cooling and discharging.
(2) Preparing a release agent for the rubber type PE protective film:
a four-necked flask polymerization system equipped with a heating device, a reflux condenser, a thermometer, a dropping funnel and a stirrer was prepared, and 54 parts of ethyl acetate was charged into the flask.
The monomer and the initiator solution are as follows by weight: the component A21.1 parts, methyl methacrylate 1.6 parts, butyl acrylate 3.5 parts, styrene 2.6 parts, acrylic acid-2-hydroxypropyl ester 1.2 parts are mixed uniformly, and AIBN 0.26 part is dissolved in the mixed monomer.
Starting a stirrer, adding 7.5 parts of mixed monomer liquid into the flask, and starting heating; the remaining monomer mixture was transferred to the dropping funnel for further use.
When the temperature of the materials in the flask rises to about 77 ℃, the reflux starts to exist, after the reflux is maintained for 40 minutes, the rest monomer mixed solution is dripped into the flask at a constant speed for 2.0 hours, and the reaction materials are kept in a reflux state in the period. After the monomer mixed solution is dropwise added, continuously maintaining the reflux state for 60 minutes, and then adding AIBN: adding 0.05 part of AIBN and 8 parts of ethyl acetate emulsion into a dropping funnel, dropping the mixture into a flask within 5 minutes, and continuously maintaining the reflux reaction for 1 hour; and (3) adding AIBN for the second time: and continuously maintaining reflux reaction for 2 hours in the same amount and operation process as the first time, and cooling and discharging to obtain the release agent for the rubber type PE protective film.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.