阅读说明：本技术 一种乙烯基全氟聚乙二醇改性弹性聚氨酯及其应用 (Vinyl perfluoropolyethylene glycol modified elastic polyurethane and application thereof ) 是由 刘鹏 于 2018-10-10 设计创作，主要内容包括：本发明涉及一种乙烯基全氟聚乙二醇改性弹性聚氨酯,其特征在于,按重量份数计,其制备方法为：在氮气保护下,在反应器中加入50-60份含乙烯基全氟聚乙二醇、6-14份二异氰酸酯单体、12-25份有机溶剂,开启搅拌将物料搅拌均匀,加热至60-90℃反应2-3h后；然后逐滴滴加0.05-0.15份催化剂,滴加完毕后60-90℃继续反应1-2h,反应过程中每0.5h测量体系-NCO百分含量,当体系达到目标-NCO百分含量为小于0.5％后,降温至室温,然后通过减压蒸馏除去有机溶剂,即得含乙烯基全氟聚乙二醇改性弹性聚氨酯。由该聚氨酯制成的爽滑且富有弹性的有机硅离型剂能够和格拉辛纸粘贴紧密,同时具有更加易于剥离的优点。(The invention relates to vinyl perfluoropolyethylene glycol modified elastic polyurethane, which is characterized in that the preparation method comprises the following steps in parts by weight: under the protection of nitrogen, adding 50-60 parts of vinyl-containing perfluoropolyethylene glycol, 6-14 parts of diisocyanate monomer and 12-25 parts of organic solvent into a reactor, starting stirring to uniformly stir the materials, heating to 60-90 ℃ and reacting for 2-3 h; and then dropwise adding 0.05-0.15 part of catalyst, continuing to react for 1-2 hours at 60-90 ℃ after dropwise adding, measuring the percentage content of-NCO in the system every 0.5 hour in the reaction process, cooling to room temperature when the percentage content of-NCO in the system reaches the target value and is less than 0.5%, and then removing the organic solvent through reduced pressure distillation to obtain the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane. The smooth and elastic organic silicon release agent prepared from the polyurethane can be tightly adhered to glassine paper, and has the advantage of easier stripping.)

1. The vinyl perfluoropolyethylene glycol modified elastic polyurethane is characterized by comprising the following components in parts by weight: under the protection of nitrogen, adding 50-60 parts of vinyl-containing perfluoropolyethylene glycol, 6-14 parts of diisocyanate monomer and 12-25 parts of organic solvent into a reactor, starting stirring to uniformly stir the materials, heating to 60-90 ℃ and reacting for 2-3 h; and then dropwise adding 0.05-0.15 part of catalyst, continuing to react for 1-2 hours at 60-90 ℃ after dropwise adding, measuring the percentage content of-NCO in the system every 0.5 hour in the reaction process, cooling to room temperature when the percentage content of-NCO in the system reaches the target value and is less than 0.5%, and then removing the organic solvent through reduced pressure distillation to obtain the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane.

2. The vinyl perfluoropolyethylene glycol modified elastomeric polyurethane as claimed in claim 1, wherein the vinyl perfluoropolyethylene glycol is at least one of allyl perfluoropolyethylene glycol and isopentenyl perfluoropolyethylene glycol, and the relative molecular weight thereof is 600-2000; the diisocyanate monomer is at least one of MDI, HDI and TDI.

3. The vinyl perfluoropolyethylene glycol modified elastomeric polyurethane according to claim 1, wherein the organic solvent is at least one of ethyl acetate, acetone, propyl acetate; the catalyst is at least one of dibutyltin dilaurate, stannous octoate, tin naphthenate and cobalt naphthenate.

4. Use of the vinyl perfluoropolyethylene glycol-modified elastic polyurethane according to any one of claims 1 to 3, characterized in that the vinyl perfluoropolyethylene glycol-modified elastic polyurethane is used in a smooth and elastic silicone release agent.

5. The use according to claim 4, characterized in that the smooth and elastic silicone release agent is formulated from the following components in parts by weight: 20-30 parts of vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane, 80-100 parts of vinyl polysiloxane, 6-12 parts of hydrogen-containing polysiloxane, 2-4 parts of anti-sticking agent, 1-3 parts of anchoring agent and 2-10 parts of platinum catalyst.

6. The use as claimed in claim 5, wherein the vinyl polysiloxane is a terminal vinyl polysiloxane having a viscosity of 2000-20000cp and a vinyl content of 0.01-0.1%; the viscosity of the hydrogenous polysiloxane is 20-50cp, and the hydrogen content is 0.3-1.2%.

7. The use of claim 5, wherein the anti-blocking agent is at least one of diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, ethylene glycol diglycidyl ester, and pentaerythritol tetraglycidyl ether.

8. The use of claim 5, wherein the anchoring agent is at least one of vinyltrimethoxysilane, vinyltris- (β -methoxyethoxy) silane, and γ - (methacryloyloxy) propyltrimethoxysilane.

9. The use according to claim 5, wherein the platinum catalyst is at least one of chloroplatinic acid-divinyltetramethyldisiloxane, chloroplatinic acid-isopropanol, chloroplatinic acid-diethyl phthalate.

10. The use according to claim 5, characterized in that the smooth and elastic silicone release agent is prepared by the following steps: adding the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane, vinyl polysiloxane, hydrogen-containing polysiloxane, anti-sticking agent and anchoring agent into a mixing device according to the formula ratio, and stirring for 15-30 min; and adding a platinum catalyst in a formula amount, and stirring for 1-5 min to obtain the smooth and elastic organic silicon mold release agent.

Technical Field

The invention belongs to the technical field of polyurethane, and relates to vinyl perfluoropolyethylene glycol modified elastic polyurethane and application thereof.

Background

The release agent composition is applied to the surface of various substrates such as paper, synthetic resin film, synthetic fiber, cloth, and the like, and cured to form a cured layer, whereby a film having releasability from an adhesive substance such as a pressure-sensitive adhesive can be formed. As such a release agent composition, one containing an organopolysiloxane having a siloxane unit containing a fluorine atom is known. The organic silicon coating is an important direction in the field of the anti-adhesion coating at present, and has the advantages of low surface tension, transparency, no toxicity, high temperature resistance, good weather resistance and the like, so that the organic silicon coating is widely applied to the surfaces of metals, ceramics, paper, plastics and textiles as the anti-adhesion coating or the anti-adhesion coating.

However, the conventional release agent composition has a problem of poor releasability from a silicone adhesive containing an organopolysiloxane such as dimethylpolysiloxane or methylphenylpolysiloxane as a main component, although it has excellent releasability from a cured film of an organic resin adhesive substance. As a result, the releasability from the silicone adhesive may become insufficient depending on the application. In the case of producing a tape-shaped release sheet or laminate by applying and curing a release agent composition, the tape-shaped release sheet or the like is usually wound into a roll shape and transported and stored in a wound state. In this case, it is known that a rolling pressure is applied to the center portion of the wound body in particular, but there is also a problem that the release layer is peeled off again from the adhesive substance by applying the rolling pressure. The invention increases the smoothness and elasticity of the release agent composition and obtains the organic silicon release agent with excellent stripping performance.

Disclosure of Invention

In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a smooth and elastic organic silicon release agent.

The invention adopts the following technical scheme that the smooth and elastic organic silicon release agent is characterized by comprising the following components in parts by weight: 20-30 parts of vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane, 80-100 parts of vinyl polysiloxane, 6-12 parts of hydrogen-containing polysiloxane, 2-4 parts of anti-sticking agent, 1-3 parts of anchoring agent and 2-10 parts of platinum catalyst.

The vinyl polysiloxane is terminal vinyl polysiloxane, the viscosity is 2000-20000cp, and the vinyl content is 0.01-0.1%; the viscosity of the hydrogenous polysiloxane is 20-50cp, and the hydrogen content is 0.3-1.2%.

The anchoring agent is at least one of vinyl trimethoxy silane, vinyl tri- (beta-methoxyethoxy) silane and gamma- (methacryloyloxy) propyl trimethoxy silane.

The platinum catalyst is at least one of chloroplatinic acid-divinyl tetramethyl disiloxane, chloroplatinic acid-isopropanol and chloroplatinic acid-diethyl phthalate.

The anti-sticking agent is at least one of 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, ethylene glycol diglycidyl ester and pentaerythritol tetraglycidyl ether.

The preparation method of the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane comprises the following steps of:

under the protection of nitrogen, adding 50-60 parts of vinyl-containing perfluoropolyethylene glycol, 6-14 parts of diisocyanate monomer and 12-25 parts of organic solvent into a reactor, starting stirring to uniformly stir the materials, heating to 60-90 ℃ and reacting for 2-3 h; and then dropwise adding 0.05-0.15 part of catalyst, continuing to react for 1-2 hours at 60-90 ℃ after dropwise adding, measuring the percentage content of-NCO in the system every 0.5 hour in the reaction process, cooling to room temperature when the percentage content of-NCO in the system reaches the target value and is less than 0.5%, and then removing the organic solvent through reduced pressure distillation to obtain the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane.

The vinyl-containing perfluoro polyethylene glycol is at least one of allyl perfluoro polyethylene glycol and isopentenyl perfluoro polyethylene glycol, and the relative molecular weight of the vinyl-containing perfluoro polyethylene glycol is 600-2000; the diisocyanate monomer is at least one of MDI, HDI and TDI; the organic solvent is at least one of ethyl acetate, acetone, butyl acetate butanone and propyl acetate; the catalyst is at least one of dibutyltin dilaurate, stannous octoate, tin naphthenate and cobalt naphthenate.

The preparation method of the smooth and elastic organic silicon release agent comprises the following steps: adding the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane, vinyl polysiloxane, hydrogen-containing polysiloxane, anti-sticking agent and anchoring agent into a mixing device according to the formula ratio, and stirring for 15-30 min; and adding a platinum catalyst in a formula amount, and stirring for 1-5 min to obtain the smooth and elastic organic silicon mold release agent.

The smooth and elastic organic silicon release agent is coated on a base material and cured at the temperature of 155-180 ℃ to obtain the release paper.

Compared with the prior art, the invention has the following advantages or beneficial results:

(1) the vinyl-containing perfluoro polyethylene glycol modified elastic polyurethane is added, and the perfluoro polyethylene glycol structure increases the oleophobicity and hydrophobicity of the organic silicon release agent, so that the organic silicon release agent is easier to peel;

(2) the toughness of the organic silicon release agent is improved due to the elasticity of the polyurethane structure, the impact resistance and the tensile resistance of the organic silicon release agent are improved, and the organic silicon release agent can be tightly attached without moving and shifting and cannot be broken when being used in the use process of release paper;

(3) the anchoring agent reacts with hydrogen-containing polysiloxane to participate in the reaction, so that the binding property of the release agent to the release paper is improved.

Detailed Description

A smooth and elastic silicone release agent of the present invention is further described below with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.

Example 1

The preparation method of the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane X comprises the following steps of:

under the protection of nitrogen, adding 54 parts of isopentene group perfluoropolyethylene glycol, 9 parts of MDI and 18 parts of acetone into a reactor, starting stirring to uniformly stir the materials, heating to 78 ℃ and reacting for 3 hours; and then dropwise adding 0.10 part of stannous octoate, continuing to react for 2 hours at 78 ℃ after dropwise adding, measuring the percentage content of-NCO in the system every 0.5 hour in the reaction process, cooling to room temperature after the percentage content of-NCO in the system reaches the target value and is less than 0.5%, and removing the organic solvent through reduced pressure distillation to obtain the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane X.

Example 2

The smooth and elastic organic silicon release agent is characterized by comprising the following components in parts by weight: the modified elastic polyurethane comprises, by weight, 30 parts of vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane, 80 parts of vinyl-terminated polysiloxane (the viscosity is 5000cp, the vinyl content is 0.04%), 12 parts of hydrogen-containing polysiloxane (the viscosity is 50cp, and the hydrogen content is 0.3%), 2 parts of ethylene glycol diglycidyl ester, 3 parts of vinyl tri- (beta-methoxyethoxy) silane and 2 parts of chloroplatinic acid-divinyl tetramethyl disiloxane.

Example 3

The smooth and elastic organic silicon release agent is characterized by comprising the following components in parts by weight: the modified elastic polyurethane comprises, by weight, 100 parts of vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane X20 parts, 100 parts of vinyl-terminated polysiloxane (the viscosity is 20000cp, the vinyl content is 0.01%), 6 parts of hydrogen-containing polysiloxane (the viscosity is 20cp, and the hydrogen content is 1.2%), 4 parts of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 1 part of gamma- (methacryloyloxy) propyl trimethoxy silane, and 10 parts of chloroplatinic acid diethyl phthalate.

Example 4

The smooth and elastic organic silicon release agent is characterized by comprising the following components in parts by weight: the modified elastic polyurethane comprises, by weight, 24 parts of vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane, 86 parts of vinyl-terminated polysiloxane (the viscosity is 2000cp, the vinyl content is 0.1%), 8 parts of hydrogen-containing polysiloxane (the viscosity is 40cp, and the hydrogen content is 0.7%), 3 parts of pentaerythritol tetraglycidyl ether, 2 parts of vinyl trimethoxy silane and 4 parts of chloroplatinic acid-isopropanol.

Examples 2-4 preparation methods of a smooth and elastic silicone release agent were: adding the vinyl-containing perfluoropolyethylene glycol modified elastic polyurethane, vinyl polysiloxane, hydrogen-containing polysiloxane, anti-sticking agent and anchoring agent into a mixing device according to the formula ratio, and stirring for 15-30 min; and adding a platinum catalyst in a formula amount, and stirring for 1-5 min to obtain the smooth and elastic organic silicon mold release agent.

Under the same conditions, the smooth and elastic organic silicon release agent and the commercial release agent (comparative example) in the examples 2-4 of the invention are coated on the glassine paper and cured at the temperature of 155 ℃ and 180 ℃ to obtain the release paper, and the performance data of the release paper obtained in the examples 2-4 and the comparative example are shown in the following table 1.

TABLE 1 Release agent Performance Table

	Example 2	Example 3	Example 4	Comparative example
					Peeling force g/mm at normal temperature	2.5	1.6	1.7	8.5
Aged peel force g/mm	2.9	1.9	2.4	11.3
					Degree of adhesion between paper and release agent	Compact	Compact	Compact	Compact

It can be seen from table 1 that both the examples and comparative examples can be adhered tightly to glassine paper, while the examples are more easily peeled off.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims.