阅读说明：本技术 一种中重剥离力的无溶剂离型硅油及其制备方法 (Medium-weight stripping force solvent-free release silicone oil and preparation method thereof ) 是由 王细平 于 2021-06-22 设计创作，主要内容包括：本发明涉及离型硅油产品,尤其涉及一种中重剥离力的无溶剂离型硅油及其制备方法,中重剥离力无溶剂离型硅油包括以下组分,乙烯基硅油、炔醇、含硬脂酰丙基的聚硅氧烷、交联剂和卡斯特催化剂。本发明所制备的无溶剂离型硅油产品对基材适应范围广,具有较高的性价比,只需极少添加量即有明显的增重效果,且稳定性好,剥离噪音小,此外本发明无溶剂离型硅油产品涂硅后剥离力衰减幅度小、残余率高。(The invention relates to a release silicone oil product, in particular to a medium-heavy peeling force solvent-free release silicone oil and a preparation method thereof. The solvent-free release silicone oil product prepared by the invention has wide application range to base materials, higher cost performance, obvious weight increasing effect with only little addition amount, good stability and low peeling noise, and in addition, the solvent-free release silicone oil product has small peeling force attenuation amplitude and high residual rate after silicon coating.)

1. The solvent-free release silicone oil with medium-weight stripping force is characterized by comprising the following components in parts by weight:

2. the medium-weight stripping force solvent-free release silicone oil as claimed in claim 1, wherein the stearyl propyl group-containing polysiloxane has a structural formula:

wherein m is more than or equal to 30 and less than or equal to 300, n is more than 0 and less than or equal to 20, and R is-CH₃Or R₁，R₁is-C₃H₆COOC₁₁H₂₃。

3. The medium-weight stripping force solvent-free release silicone oil as claimed in claim 2, wherein the stearyl propyl group-containing polysiloxane is synthesized by the following formula in parts by weight:

4. the medium-weight stripping force solvent-free release silicone oil as claimed in claim 1 or 2, wherein the viscosity of the vinyl silicone oil is 800-1200 mPa-s, and the mass fraction of vinyl groups in the vinyl silicone oil is 0.5-2%.

5. The medium-weight stripping force solvent-free release silicone oil as claimed in claim 4, wherein the structural formula of the vinyl silicone oil is as follows:

wherein m is more than or equal to 50 and less than or equal to 500, and n is more than or equal to 0 and less than or equal to 50.

6. The medium-weight stripping force solvent-free release silicone oil as claimed in claim 5, wherein the vinyl silicone oil is prepared from the following synthetic formula in parts by weight:

7. the medium-weight stripping force solvent-free release silicone oil according to claim 5, wherein the cross-linking agent is polymethylhydrosilane and has a viscosity of 20 mPas.

8. The medium-weight stripping force solvent-free release silicone oil as claimed in claim 5, further comprising fluorine-containing hydride siloxane, wherein the mass fraction of the fluorine-containing hydride siloxane in the medium-weight stripping force solvent-free release silicone oil is 0.01-2%.

9. The medium-weight stripping force solvent-free release silicone oil as claimed in claim 8, wherein the formula of the fluorine-hydrogen-containing siloxane is (CH)₃)₃SiO-[-(CH₃)RSiO-]_a-[-(CH₃)HSiO-]_b-Si(CH₃)₃Wherein R is-CH₂CH₂CF₂CF₂CF₂CF₃A is more than or equal to 12 and less than or equal to 15, and b is more than or equal to 20 and less than or equal to 30.

10. The preparation method of the medium-weight stripping force solvent-free release silicone oil according to claim 8, characterized by comprising the following steps:

(1) synthesis of vinyl silicone oil: mixing octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane, controlling vacuum degree and introducing N₂Distilling the distillate generated by the reaction, then adding tetramethyl divinyl disiloxane and tetramethyl ammonium hydroxide alkali gel for reaction, breaking the tetramethyl ammonium hydroxide alkali gel after the reaction is finished, and then heating to remove low-boiling-point substances to prepare the vinyl silicone oil;

(2) synthesis of stearoyl propyl group-containing polysiloxane: under the protection of nitrogen, mixing and stirring hydrogen-containing silicone oil, toluene and chloroplatinic acid-isopropanol solution, slowly dripping lauryl acrylate for reaction, removing the toluene by reduced pressure distillation after the reaction is finished, continuously heating and vacuumizing to remove low-boiling-point substances, and preparing and obtaining the polysiloxane containing stearoyl propyl;

(3) preparing release silicone oil: uniformly mixing vinyl silicone oil, alkynol, stearyl propyl group-containing polysiloxane and fluorine-hydrogen-containing siloxane, and then adding a cross-linking agent and a Kaster catalyst to prepare the solvent-free release silicone oil.

Technical Field

The invention relates to a release silicone oil product, in particular to a medium-weight stripping force solvent-free release silicone oil and a preparation method thereof.

Background

The release silicone oil comprises the following components: solvent-type release silicone oil, solvent-free silicone oil and emulsion-type release silicone oil. The solvent-type release silicone oil contains a solvent, and a large amount of solvent is required to be added in the use process, so that the solvent-type release silicone oil has great harm to the environment and personnel and is gradually eliminated; the emulsion type release silicone oil is small in application range at present and poor in adaptability to paper, especially glassine paper base materials; the solvent-free release silicone oil has wide adaptability, particularly has good adaptability to various paper substrates, is nontoxic and pollution-free, does not need a solvent in the using process, has no pollution to the environment and no toxic action on personnel, and becomes the most main direction for the market application of the release silicone oil.

The solvent-free release silicone oil can be classified into the following types according to its peeling force: ultra light peel force (1-3 grams), light peel force (8-13 grams), medium heavy peel force (15-30 grams), heavy peel force (35-60 grams), ultra heavy peel force (> 70 grams). At present, release paper products are more and more diversified, release paper with different peeling forces is required, the whole industry gradually enters subdivision, and therefore the requirements on release silicone oil are more and more delicate, so how to develop a solvent-free release silicone oil with high cost performance, good peeling stability, obvious peeling weight increasing effect and extremely small addition amount, break through the blank period of domestic release silicone oil products, and become the main requirements of the market.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the solvent-free release silicone oil with medium-weight stripping force, and the solvent-free release silicone oil with medium-weight stripping force is synthesized into the stearyl propyl-containing polysiloxane to be used as the heavy-weight stripping additive of the solvent-free release silicone oil, so that the silicone oil has the advantages of obvious silicone oil stripping force weight increasing effect, good stability, small stripping noise, extremely small addition amount and high cost performance. Meanwhile, the solvent-free release silicone oil product has wide application range to base materials, can be suitable for silicon coating of paper base materials such as PEK, glassine and CKK, and has small attenuation amplitude of stripping force and high residual rate after silicon coating.

The technical purpose of the invention is realized by the following technical scheme that the release silicone oil with medium-weight stripping force comprises the following components in parts by weight:

in the invention, the structural formula of the stearoyl propyl group-containing polysiloxane is as follows:

wherein m is more than or equal to 30 and less than or equal to 300, n is more than 0 and less than or equal to n20, R is-CH₃Or R₁，R₁is-C₃H₆COOC₁₁H₂₃。

In the invention, the synthesis formula of the stearoyl propyl group-containing polysiloxane is as follows according to parts by weight:

in the invention, the viscosity of the vinyl silicone oil is 800-1200mPa & s, and the mass fraction of vinyl in the vinyl silicone oil is 0.5-2%.

Further, the structural formula of the vinyl silicone oil is as follows:

wherein m is more than or equal to 50 and less than or equal to 500, and n is more than or equal to 0 and less than or equal to 50.

Further, in the vinyl silicone oil, the synthetic formula is as follows according to parts by weight:

in the invention, the cross-linking agent is polymethylhydrosilane, and the viscosity is 20mPa & s.

In the invention, the silicone release agent also comprises fluorine-containing hydrogen-based siloxane, and the mass fraction of the fluorine-containing hydrogen-based siloxane in the medium-weight stripping force solvent-free release silicone oil is 0.01-2%.

Further, the structural formula of the fluorine-hydrogen-containing siloxane is (CH)₃)₃SiO-[-(CH₃)RSiO-]_a-[-(CH₃)HSiO-]_b-Si(CH₃)₃Wherein R is-CH₂CH₂CF₂CF₂CF₂CF₃A is more than or equal to 12 and less than or equal to 15, and b is more than or equal to 20 and less than or equal to 30.

The invention also aims to provide a preparation method of the solvent-free release silicone oil with medium-heavy peeling force, which comprises the following steps:

(1) synthesis of vinyl silicone oil: mixing octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane, controlling vacuum degree and introducing N₂Distilling the distillate generated by the reaction, then adding tetramethyl divinyl disiloxane and tetramethyl ammonium hydroxide alkali gel for reaction, breaking the tetramethyl ammonium hydroxide alkali gel after the reaction is finished, and then heating to remove low-boiling-point substances to prepare the vinyl silicone oil;

(2) synthesis of stearoyl propyl group-containing polysiloxane: under the protection of nitrogen, mixing and stirring hydrogen-containing silicone oil, toluene and chloroplatinic acid-isopropanol solution, slowly dripping lauryl acrylate for reaction, removing the toluene by reduced pressure distillation after the reaction is finished, continuously heating and vacuumizing to remove low-boiling-point substances, and preparing and obtaining the polysiloxane containing stearoyl propyl;

(3) preparing release silicone oil: uniformly mixing vinyl silicone oil, alkynol, polysiloxane containing stearoyl propyl and fluorine-containing hydrogen siloxane, and then adding a cross-linking agent and a Caster catalyst to prepare the solvent-free release silicone oil.

The invention has the following beneficial effects:

(1) according to the invention, the stearoyl propyl-containing polysiloxane is synthesized and used as a peeling force regulator of release silicone oil, the addition amount is very small, the cost performance is high, the peeling force of the release silicone oil is greatly increased, the stability of the peeling force is good, and the peeling noise is low;

(2) according to the invention, the weight increment of the peeling force is further improved by compounding the polysiloxane containing the stearoyl propyl group and the siloxane containing the fluorine-hydrogen group, and the release paper product with the overweight peeling force can be prepared;

(3) the release silicone oil product coating prepared by the invention has wide application range to base materials, can be suitable for silicon coating of paper base materials such as PEK, glassine and CCK, and has small attenuation amplitude of stripping force and high residual rate.

Detailed Description

Example 1

99.8 parts of vinyl silicone oil, 0.2 part of alkynol, 0.5 part of stearyl propyl-containing polysiloxane, 4.3 parts of a cross-linking agent and 1.5 parts of a Kaster catalyst.

In this example, vinyl silicone oil and alkynol are the main agents of the solventless release silicone oil.

Wherein the viscosity of the vinyl silicone oil is 1000 mPas, and the mass fraction of the vinyl is 1%.

Wherein the structural formula of the vinyl silicone oil is shown in the specification

Wherein m is more than or equal to 50 and less than or equal to 500, and n is more than or equal to 0 and less than or equal to 50.

Further, in this example, the average structural formula of the vinyl silicone oil used is

Wherein, in the vinyl silicone oil, the synthetic formula is as follows according to the weight portion: 1255.2 parts of octamethylcyclotetrasiloxane, 32.7 parts of tetramethyltetravinylcyclotetrasiloxane, 12.1 parts of tetramethyldivinyldisiloxane and 7 parts of tetramethylammonium hydroxide alkali gel.

In the embodiment, the stearyl propyl group-containing polysiloxane is a heavy-stripping additive for preparing the solvent-free release silicone oil, and the stearyl propyl group-containing polysiloxane adopted in the embodiment has the advantages of obvious stripping force weight increasing effect, good stripping force stability, small addition amount and high cost performance.

Wherein, the structural formula of the stearoyl propyl-containing polysiloxane is shown in the specificationWherein m is more than or equal to 30 and less than or equal to 300, n is more than 0 and less than or equal to 20, and R is-CH₃Or R₁，R₁is-C₃H₆COOC₁₁H₂₃。

Further, in this example, the structural formula of the stearoyl propyl group-containing polysiloxane is shown in the specification

Wherein, in the stearyl propyl group-containing polysiloxane, the synthetic formula is as follows according to parts by weight: 732.4 parts of hydrogen-containing silicone oil, 433.5 parts of lauryl acrylate, 200 parts of toluene and 1 part of chloroplatinic acid-isopropanol solution.

Wherein the concentration of platinum in the chloroplatinic acid-isopropanol solution is 4000 ppm.

Wherein the cross-linking agent is polymethylhydrosiloxane, and the viscosity of the polymethylhydrosiloxane is 20mPa & s.

Wherein the Kaster catalyst is used for preparing release silicone oil and contains platinum with the concentration of 5000 ppm.

Wherein the alkynol is ethynyl cyclohexanol.

The preparation method of this example is as follows:

(1) synthesis of vinyl silicone oil: adding octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane into three-neck flask, stirring, heating to 65 ℃, and introducing N₂While reducing the pressure to control the vacuum degree to-0.09 Mpa, regulating N₂The flow rate is controlled so that the distillate is 0.5 part/min and lasts for 30 min; then introducing tetramethyl divinyl disiloxane and tetramethyl ammonium hydroxide alkali gel, stirring and heating to 100-105 ℃, and carrying out polymerization reaction for 4 hours; heating to 150 deg.C, reacting for 2h to remove tetramethylammonium hydroxide alkali gel, heating to 190 deg.C, controlling vacuum degree to-0.098 Mpa, and introducing N₂Removing low-boiling-point substances until no distillate is obtained, and preparing the vinyl silicone oil;

(2) synthesis of stearoyl propyl group-containing polysiloxane: in N₂Adding hydrogen-containing silicone oil, toluene and chloroplatinic acid-isopropanol solution into a three-neck flask under protection, stirring at room temperature, slowly dripping dodecyl acrylate through a dropping funnel for 2 hours, heating to 60 ℃ after dripping is finished, and reacting for 8 hours; heating to 110 ℃, distilling under reduced pressure to remove toluene, continuously heating to 170 ℃, vacuumizing to remove low-boiling-point substances until no distillate exists, and preparing the stearoyl propyl-containing polysiloxane;

(3) preparing release silicone oil: uniformly mixing vinyl silicone oil, alkynol and polysiloxane containing stearoyl propyl, and then adding polymethylhydrosiloxane and a Kaster catalyst to prepare the solvent-free release silicone oil.

Example 2

This example differs from example 1 in that:

97.6 parts of vinyl silicone oil, 0.4 part of alkynol, 1 part of stearoyl propyl-containing polysiloxane, 4.4 parts of a crosslinking agent and 1 part of a Karster catalyst.

Wherein the viscosity of the vinyl silicone oil is 800 mPas, and the mass fraction of the vinyl is 0.5%.

Wherein, in the vinyl silicone oil, the synthetic formula is as follows according to the weight portion: 1200 parts of octamethylcyclotetrasiloxane, 11 parts of tetramethyltetravinylcyclotetrasiloxane, 10 parts of tetramethyldivinyldisiloxane and 5 parts of tetramethylammonium hydroxide alkali gel.

Wherein, in the stearyl propyl group-containing polysiloxane, the synthetic formula is as follows according to parts by weight: 710 parts of hydrogen-containing silicone oil, 410 parts of lauryl acrylate, 180 parts of toluene and 2 parts of chloroplatinic acid-isopropanol solution.

The preparation method of this example differs from that of example 1 in that: adding tetramethyltetravinylcyclotetrasiloxane, stirring, heating to 70 ℃, adding tetramethylammonium hydroxide alkali gel, stirring, heating to 105 ℃, carrying out polymerization reaction for 5 hours, removing the tetramethylammonium hydroxide alkali gel, and heating to 200 ℃; in the step (2), after the dodecyl acrylate is dropwise added, the temperature is raised to 65 ℃, the reaction is carried out for 10 hours, then the temperature is raised to 120 ℃, the toluene is removed by reduced pressure distillation, and then the temperature is raised to 180 ℃, and the low-boiling-point substances are removed by vacuum pumping.

Example 3

This example differs from example 1 in that:

101.6 parts of vinyl silicone oil, 0.4 part of alkynol, 0.5 part of stearyl propyl-containing polysiloxane, 4 parts of a crosslinking agent, 1.5 parts of a Karster catalyst and fluorine-containing hydrogen siloxane.

Wherein the viscosity of the vinyl silicone oil is 1200 mPas, and the mass fraction of the vinyl is 2%.

Wherein, in the vinyl silicone oil, the synthetic formula is as follows according to the weight portion: 1300 parts of octamethylcyclotetrasiloxane, 85 parts of tetramethyltetravinylcyclotetrasiloxane, 15 parts of tetramethyldivinyldisiloxane and 8 parts of tetramethylammonium hydroxide alkali gel.

Wherein, in the stearyl propyl group-containing polysiloxane, the synthetic formula is as follows according to parts by weight: 750 parts of hydrogen-containing silicone oil, 450 parts of lauryl acrylate, 220 parts of toluene and 2 parts of chloroplatinic acid-isopropanol solution.

Wherein the mass fraction of the fluorine-hydrogen-containing siloxane in the medium-weight stripping force solvent-free release silicone oil is 0.01-2%. The fluorine-hydrogen-containing siloxane is used as a heavy stripping regulator for preparing release silicone oil, and the structural formula of the fluorine-hydrogen-containing siloxane is (CH)₃)₃SiO-[-(CH₃)RSiO-]_a-[-(CH₃)HSiO-]_b-Si(CH₃)₃. Wherein R is-CH₂CH₂CF₂CF₂CF₂CF₃Wherein a is more than or equal to 12 and less than or equal to 15, and b is more than or equal to 20 and less than or equal to 30.

In the embodiment, the fluorine-containing alkyl siloxane and the polysiloxane containing the stearyl propyl group are used together as the heavy peeling regulator, the peeling force increment is larger than that of the sole use of the polysiloxane containing the stearyl propyl group, and the release paper product with the overweight peeling force can be prepared.

The preparation method of this example differs from that of example 1 in that: in the step (3), the mixture of the fluorine-containing alkyl siloxane and the stearyl propyl group-containing polysiloxane is added into the vinyl silicone oil and the alkynol.

Comparative example 1

Comparative example 1 differs from example 1 in that:

99.8 parts of vinyl silicone oil, 0.2 part of alkynol, 4.3 parts of cross-linking agent and 1.5 parts of Kaster catalyst.

No stearoyl propyl-containing polysiloxane was added in this comparative example.

Comparative example 2

Comparative example 2 differs from example 1 in that:

99.8 parts of vinyl silicone oil, 0.2 part of alkynol, 0.5 part of fluorine-hydrogen-containing siloxane, 4.3 parts of a crosslinking agent and 1.5 parts of a Karster catalyst.

In this comparative example, a fluorochemical siloxane was used in place of the stearyl propyl group-containing polysiloxane.

COMPARATIVE EXAMPLE 3 (CONTROL)

Comparative example 3 a commercially available heavy peeling force solventless release silicone oil was used, and the coating formulation was: 60 parts of main agent, 40 parts of heavy stripping additive, 6.5 parts of cross-linking agent and 2.5 parts of platinum catalyst with the platinum concentration of 5000 ppm.

The release silicone oils prepared in examples 1 to 3 and comparative examples 1 to 3 were applied to 60g/m each²The silicon coating amount on the heavy glassine paper is 1.2g/m²Baking at 140 ℃ for 15 seconds, putting the cured silicon-coated release paper into a constant-temperature constant-humidity box, comparing at 85 ℃ and 85% humidity, measuring the stripping force of the silicon-coated glassine paper by using a TESA 7475 adhesive tape, and the stripping force after being placed for 15 days, wherein the NITTO 31B test standard refers to FTM10 of FINAT technical handbook, and finally obtaining the product performance, which is shown in the following table:

the foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is conceivable, and the examples presented herein demonstrate the results of applicants' actual experiments. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.