CN107556471A - A kind of non-isocyanate organic silicon polyurethane block copolymer and its synthetic method - Google Patents

Abstract

The invention relates to a non-isocyanate organosilicon-polyurethane block copolymer and a synthesis method thereof. Specifically, the addition polymerization reaction of α, ω-aminoalkyl polysiloxane and cyclocarbonate in a solvent is carried out. The non-isocyanate organosilicon-polyurethane block copolymer prepared by the present invention avoids the use of toxic raw material diisocyanate, the production process and products are safe and environmentally friendly, and the hydroxyl group on the carbon atom at the β position in the urethane chain segment can form with its carbonyl group Intramolecular hydrogen bond, with strong molecular force, the hydrolysis resistance, chemical resistance and permeability resistance of the copolymer are more excellent, and the block copolymer molecule can be adjusted according to the chain length of polysiloxane and the structure of cyclocarbonate The structure is designed to meet its application in anti-fouling flash coating, leather, textile, paper, fiber processing, medical equipment and other fields.

Description

A kind of non-isocyanate silicone-polyurethane block copolymer and its synthesis method

technical field

The invention belongs to the technical field of organosilicon polymers, in particular to a non-isocyanate organosilicon-polyurethane block copolymer and a synthesis method thereof.

Background technique

Polysiloxane-polyurethane block copolymers are a class of promising polymer materials. From the perspective of molecular segment structure, the polysiloxane segment can provide excellent thermal stability, dielectric properties, flexibility, water resistance, air permeability and biocompatibility; the polyurethane segment can provide good mechanical properties, abrasion resistance etc. Therefore, this material not only overcomes the shortcomings of polysiloxane's poor mechanical properties, but also makes up for the shortcomings of polyurethane's poor weather resistance, and has good water resistance, low temperature flexibility, surface accumulation, dielectric properties and excellent biophase properties. Capacitive, it has great application potential in anti-fouling flash coating, leather, textile, paper making, fiber processing, medical equipment and other fields.

At present, there are generally two synthetic methods of silicone-polyurethane block copolymers: one is the reaction of hydroxyalkyl polysiloxane and diisocyanate; the other is the reaction of aminoalkyl polysiloxane and diisocyanate. reaction. Both of the above two synthetic methods require diisocyanate as a raw material, and isocyanate is a toxic substance that is very harmful to the human body, and isocyanate is sensitive to moisture in the environment, which is not in line with the development direction of safety and environmental protection. In recent years, with the increasingly prominent environmental problems and the increasing scarcity of petroleum resources, green environmental protection, low-carbon and high-efficiency have become the main development direction of the polyurethane industry. Various renewable biomass-based polyurethanes and water-based polyurethanes are emerging, but these are all The critical issue of isocyanate use is not addressed.

Huang Yaocheng et al.'s research on "Synthesis and Application of Non-isocyanate Polyurethane" used cyclocarbonate compounds and primary amines to prepare polyurethanes, but the reaction generally used two-membered cyclocarbonates and dibasic primary amines. The short chain of primary amines The structure greatly limits the polymerization efficiency and the introduction of target functional groups in high molecular weight polymers.

Contents of the invention

In order to overcome the above disadvantages, the present invention provides a non-isocyanate silicone-polyurethane block copolymer and a synthesis method thereof. Using cyclocarbonate to react with polysiloxane, it does not use diisocyanate as raw material, the production process and product itself are safe and environmentally friendly, and the hydroxyl group on the carbon atom at the β position in the urethane chain segment can form an intramolecular hydrogen bond with its carbonyl group , has strong intermolecular force, and the copolymer has more excellent hydrolysis resistance, chemical resistance and permeability resistance; the synthesis method is simple, efficient, strong in practicability, and easy to popularize.

To achieve the above object, the present invention adopts the following scheme:

A non-isocyanate silicone-polyurethane block copolymer, the copolymer uses cyclocarbonate or cyclocarbonate-containing disiloxane as the hard segment and polysiloxane as the soft segment.

In order to overcome the problem of single polymer structure and low synthesis efficiency of the existing reaction system of dicyclic carbonate and dibasic primary amine, the present invention accidentally found in the research: replace the existing dibasic primary polysiloxane with amino-terminated polysiloxane Amines, while successfully introducing polysiloxane segments, improved the polymerization of cyclic carbonates and amino groups, and the prepared non-isocyanate silicone-polyurethane block copolymers were more resistant to hydrolysis than isocyanate silicone-polyurethane block copolymers. , chemical resistance and impermeability are more excellent.

Preferably, the structural formula of the copolymer is any one of the following:

Wherein, n and x are natural numbers greater than zero, and R ₁ or R ₂ is one or more of methyl, ethyl, vinyl, phenyl, and trifluoropropyl.

Preferably, the structural formula of R ₂ is -CH ₂ -CH ₂ -CH ₂ -.

The present invention also provides a kind of synthetic method of non-isocyanate silicone-polyurethane block copolymer, comprising:

The non-isocyanate silicone-polyurethane block copolymer is synthesized by reacting cyclocarbonate or cyclocarbonate-containing disiloxane and polysiloxane in a solvent.

Preferably, the structural formula of the cyclocarbonate is:

Wherein, R ₁ is one or a combination of hydrogen, methyl, phenyl or benzyl.

Preferably, the solvent is one or a combination of dioxane, tetrahydrofuran, ethyl acetate, N,N-dimethylformamide, isopropanol, toluene or acetone.

Preferably, the reaction conditions are: react at room temperature for 1 to 8 hours;

Preferably, the molar ratio of the organosiloxane to the cyclocarbonate is 1:1.

Preferably, the synthesis method of the disiloxane containing cyclic carbonic acid is: carry out the hydrosilylation reaction between the cyclic carbonate containing vinyl and tetramethyldihydrodisiloxane under the karstedt catalyst, to obtain .

The present invention also provides the non-isocyanate silicone-polyurethane block copolymer prepared by any one of the above-mentioned methods.

The present invention also provides the application of cyclocarbonate or disiloxane containing cyclocarbonate in the preparation of non-isocyanate silicone-polyurethane block copolymer.

Beneficial effects of the present invention

1) The present invention avoids the use of toxic raw material diisocyanate, and the production process and product itself are safe and environmentally friendly; the hydroxyl group on the β-position carbon atom in the carbamate chain segment can form an intramolecular hydrogen bond with its carbonyl group, and has a strong intermolecular The hydrolysis resistance, chemical resistance and permeation resistance of the copolymer are more excellent; the molecular structure of the block copolymer can be designed according to the chain length of polysiloxane and the structure of cyclocarbonate to meet the requirements of different application fields. Require;

2) The synthetic method of the present invention is simple and efficient, has strong practicability, and is easy to popularize.

detailed description

The features of the present invention and other relevant features are described in further detail below through the embodiments, so as to facilitate the understanding of those skilled in the art:

A non-isocyanate silicone-polyurethane block copolymer is characterized in that the block copolymer structural formula is

Wherein, n and x are natural numbers greater than zero.

Preferably, the R is one or more of methyl, ethyl, vinyl, phenyl, and trifluoropropyl.

Preferably, the structural formula of R ₂ is -CH ₂ -CH ₂ -CH ₂ -.

Preferably, the structural formula of the cyclocarbonate is:

Wherein, R is _one or a combination of hydrogen, methyl, phenyl or benzyl;

Preferably, the solvent for the reaction is one or a combination of dioxane, tetrahydrofuran, ethyl acetate, N,N-dimethylformamide, isopropanol, toluene or acetone;

Preferably, the reaction time is 1-8 hours.

Preferably, the molar ratio of α,ω-aminoalkyl polyorganosiloxane to cyclocarbonate in the reaction is 1:1.

The present invention also provides a synthetic method of disiloxane containing cyclic carbonic acid, wherein the cyclic carbonate containing vinyl and tetramethyldihydrogen disiloxane are subjected to a hydrosilylation reaction under a karstedt catalyst, i.e. have to.

The present invention also provides the non-isocyanate silicone-polyurethane block copolymer prepared by any one of the above methods.

The non-isocyanate silicone-polyurethane block copolymers described in any of the above can be used in the preparation of anti-fouling flash coatings, leather, textile materials, paper materials, fiber treatment agents, medical devices and other fields, and the synthesized products can meet related needs of the industry.

The present invention also provides a better synthetic method of non-isocyanate silicone-polyurethane block copolymer, comprising: at room temperature, α, ω-aminoalkylpolysiloxane and cyclocarbonate react in a solvent for 1～ After 12 hours, the solvent was removed by heating to obtain a non-isocyanate silicone-polyurethane block copolymer.

Example 1

α,ω-Aminoalkylpolysiloxane 10.0g with cyclocarbonate 1.2g (guaranteed an equimolar ratio of amino group to cyclocarbonate), mixed uniformly in a dioxane solvent, reacted at room temperature for 6h, and then heated to remove the solvent to obtain a non-isocyanate silicone-polyurethane block copolymer.

The _Mn obtained by GPC is 8315, the _Mw is 14634, and the molecular weight distribution index is 1.76.

Example 2

The procedure described in Example 1 was repeated except that the α,ω-aminoalkylpolysiloxane was

The _Mn obtained by GPC is 7968, the _Mw is 15697, and the molecular weight distribution index is 1.97.

Example 3

The procedure described in Example 1 was repeated except that the α,ω-aminoalkylpolysiloxane was

The _Mn obtained by GPC is 9324, the _Mw is 17156, and the molecular weight distribution index is 1.84.

Example 4

The procedure described in Example 1 was repeated except that the α,ω-aminoalkylpolysiloxane was

The _Mn obtained by GPC is 9167, the _Mw is 15859, and the molecular weight distribution index is 1.73.

Example 5

The procedure described in Example 1 was repeated except that the α,ω-aminoalkylpolysiloxane was

The _Mn obtained by GPC is 8654, the _Mw is 15663, and the molecular weight distribution index is 1.81.

Example 6

The procedure described in Example 1 was repeated except that the α,ω-aminoalkylpolysiloxane was

GPC shows that M _n is 8279, M _w is 15316, and the molecular weight distribution index is 1.85.

Example 7

The steps described in Example 1 were repeated, except that the reaction time was 3 h.

The _Mn obtained by GPC is 8298, the _Mw is 15102, and the molecular weight distribution index is 1.82.

Example 8

The steps described in Example 1 were repeated, except that the reaction time was 9 h.

The _Mn obtained by GPC was 8362, the _Mw was 14634, and the molecular weight distribution index was 1.75.

Example 9

Repeat the steps described in Example 1, except that the cyclocarbonate is

The _Mn obtained by GPC is 9563, the _Mw is 17596, and the molecular weight distribution index is 1.84.

Example 10

Repeat the steps described in Example 1, except that the cyclocarbonate is

The _Mn obtained by GPC is 9154, the _Mw is 16294, and the molecular weight distribution index is 1.78.

Example 11

Repeat the steps described in Example 1, except that the cyclocarbonate is

The _Mn obtained by GPC is 8498, the _Mw is 6146, and the molecular weight distribution index is 1.90.

Finally, it should be noted that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still The technical solutions described in the foregoing embodiments may be modified, or part of them may be equivalently replaced. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention. Although the specific implementation of the present invention has been described above, it is not a limitation to the protection scope of the present invention. Those skilled in the art should understand that on the basis of the technical solution of the present invention, those skilled in the art can do it without creative work. Various modifications or deformations are still within the protection scope of the present invention.

Claims (10)

1. A non-isocyanate silicone-polyurethane block copolymer, characterized in that the copolymer uses cyclocarbonate or disiloxane containing cyclocarbonate as hard segment and polysiloxane as soft segment respectively. 2. copolymer as claimed in claim 1, is characterized in that, the structural formula of described copolymer is following any one: Wherein, n and x are natural numbers greater than zero, and R ₁ or R ₂ is one or more of methyl, ethyl, vinyl, phenyl, and trifluoropropyl. 3. copolymer as claimed in claim 1, is characterized in that, described R _The structural formula is. 4. A synthetic method of non-isocyanate silicone-polyurethane block copolymer, characterized in that, comprising: The non-isocyanate silicone-polyurethane block copolymer is synthesized by reacting cyclocarbonate or cyclocarbonate-containing disiloxane and polysiloxane in a solvent. 5. the method for claim 3 is characterized in that, described cyclocarbonate structural formula is: Wherein, R ₁ is one or a combination of hydrogen, methyl, phenyl or benzyl. 6. The method according to claim 3, wherein the solvent is one of dioxane, THF, ethyl acetate, N,N-dimethylformamide, Virahol, toluene or acetone one or a combination of several. 7. The method according to claim 3, characterized in that, the reaction conditions are: react at room temperature for 1 to 8 hours; Or the molar ratio of the organosiloxane to the cyclocarbonate is 1:1. 8. method as claimed in claim 3, is characterized in that, the synthetic method of described disiloxane containing ring carbonic acid is that ring carbonate containing vinyl and tetramethyl dihydrogen base disiloxane are in karstedt Catalyst for hydrosilylation reaction. 9. The non-isocyanate silicone-polyurethane block copolymer prepared by the method according to any one of claims 4-8. 10. Use of cyclocarbonate or cyclocarbonate-containing disiloxane in the preparation of non-isocyanate silicone-polyurethane block copolymers.