CN105461889B - Medical transparent high-strength polyurethane adhesive of one kind and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical fields of adhesive, disclose medical transparent high-strength polyurethane adhesive of one kind and preparation method thereof.The adhesive for polyurethane is prepared by the following raw material counted in parts by weight：20~200 parts of polyester diol or polyether Glycols, 40~200 parts of diisocyanate, 0.02~0.06 part of catalyst, 3~20 parts of chain extender, 30~60 parts of organic solvent.The adhesive of the present invention has very high transparency and very strong peel strength, and is suitable for low temperature environment.The adhesive of the present invention can be used as medical adhesive.

Description

A kind of medical transparent high-strength polyurethane adhesive and preparation method thereof

technical field

The invention belongs to the technical field of adhesives and relates to a polyurethane material, in particular to a medical transparent high-strength polyurethane adhesive and a preparation method thereof.

Background technique

Adhesives are essential materials for the development of modern industry and the improvement of life. Adhesive technology plays an important role in modern economy, modern national defense and modern science and technology. With the continuous development of China's economy and the steady improvement of people's living standards, the demand for adhesives is increasing year by year. There is no doubt that there is fierce competition and unlimited hope in the field of adhesives.

Polyurethane adhesives have excellent shear strength and impact resistance properties, are suitable for various structural bonding fields, and have excellent flexibility properties.

Polyurethane adhesive has excellent rubber properties and can adapt to the bonding of substrates with different thermal expansion coefficients. It forms a soft-hard transition layer between substrates, which not only has strong adhesion, but also has excellent cushioning and shock absorption. Function. The low and ultra-low temperature performance of polyurethane adhesives exceeds that of all other types of adhesives.

Existing medical adhesives not only require the adhesive to have strong peel strength, but also require safety and non-toxicity. However, many current medical adhesives have poor low temperature resistance and low solid content, and their cohesiveness will be greatly reduced under low temperature conditions or when there is too much water. The polyurethane adhesive prepared by the invention is dried with its organic solvent after use to obtain a safe, non-toxic and hydrophobic medical adhesive.

To sum up, it is an urgent problem to solve the problems of low temperature resistance and solid content of the adhesive, so as to form a high-strength adhesive.

Contents of the invention

In order to overcome the shortcomings and deficiencies in the prior art, the object of the present invention is to provide a medical transparent high-strength polyurethane adhesive.

Another object of the present invention is to provide a method for preparing the above-mentioned medical transparent high-strength polyurethane adhesive.

The object of the present invention is achieved through the following technical solutions:

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight:

The polyester diol or polyether diol is one of polytetrahydrofuran diol, polycaprolactone diol, polyoxypropylene ether diol, succinic acid polyester diol or polypropylene oxide more than one species.

The number average molecular weight of the polyester diol or polyether diol is 1000-5000.

The diisocyanate is at least one of toluene diisocyanate, hexamethylene diisocyanate, dimethylmethane diisocyanate or xylylene diisocyanate.

The chain extender is more than one of 1,4-butanediol, γ-glycidyl etheroxypropyltrimethoxysilane or glycidyl methacrylate.

The catalyst is at least one of stannous octoate, dibutyltin dilaurate or dimethylcyclohexylamine.

The organic solvent is at least one of N,N-dimethylformamide, benzene, xylene or cyclohexanone.

The preparation method of the medical transparent high-strength polyurethane adhesive specifically comprises the following steps:

(1) dehydrating polyester diol or polyether diol to obtain a dehydrated polymer;

(2) Add catalyst, organic solvent and diisocyanate to the dehydrated polymer in step (1) under the condition of feeding inert gas and stirring, and react at 60-80° C. for 3-4 hours to obtain a prepolymer;

(3) Adding a chain extender to the prepolymer in step (2), reacting at 60-80° C. for 6-7 hours to obtain a polyurethane adhesive. During this period, according to the difference of viscosity, adjust the rotation speed of the agitator and add an appropriate amount of organic solvent at any time.

The conditions for the dehydration treatment in step (1) are that the stirring speed is 800-1200 r/min, the temperature is 105-115°C, the vacuum degree is 0.08-0.16Mpa, and the dehydration treatment is 1-3 hours.

The stirring speed in step (2) is 600-800 r/min; the inert gas is nitrogen.

The transparency of the medical transparent high-strength polyurethane adhesive of the present invention can reach 55%-75%, the tensile strength is 3-8MPa, the tear strength is ^{9-12kN.m -1.} The elongation at break is 110%-200%, High peel strength, cured at 20-60°C; can withstand -5°C-100°C environment.

Compared with the prior art, the present invention has the following advantages:

The adhesive of the invention has high transparency and strong peeling strength, and is suitable for low temperature environment.

Detailed ways

The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

Example 1

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight: 20 parts of polytetrahydrofuran diol, 40 parts of hexamethylene diisocyanate, 20 parts of chain extender 1,4-butanediol, catalyst 0.02 part of dibutyltin dilaurate, 40 parts of organic solvent N,N-dimethylformamide.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of polytetrahydrofuran diol (its molecular weight is 2000) (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours), and the dehydration polymerization is obtained. thing;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dibutyltin dilaurate and organic solvent N to the dehydrated polymer in step (1) at 80°C , N-dimethylformamide, after stirring evenly, add hexamethylene diisocyanate, react for 4h, and make a prepolymer; (the catalyst can be made into a toluene solution before adding),

(3) Add chain extender 1,4-butanediol to the prepolymer in step (2), and react at 80° C. for 6 hours to obtain a polyurethane adhesive.

The obtained polyurethane adhesive has a number average molecular weight of 20000, a transparency of 60%, a tensile strength of 3.5MPa, a tear strength of 10kN·m ^-1 , an elongation at break of 130%, and a solid content of 65%.

Example 2

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight: 50 parts of polytetrahydrofuran diol (molecular weight 1000), 40 parts of hexamethylene diisocyanate, 10 parts of chain extender glycidyl methacrylate parts, catalyst dibutyltin dilaurate 0.04 parts, solvent N,N-dimethylformamide 40 parts.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of polytetrahydrofuran diol (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours) to obtain a dehydrated polymer;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dibutyltin dilaurate, organic solvent N to the dehydrated polymer of step (1) at 80°C , N-dimethylformamide, stirring evenly, adding hexamethylene diisocyanate, reacting for 4 hours, to obtain a prepolymer;

(3) Add chain extender glycidyl methacrylate to the prepolymer in step (2), and react at 80°C for 6 hours to obtain polyurethane adhesive.

The obtained polyurethane adhesive has a number average molecular weight of 18000, a transparency of 65%, a tensile strength of 3MPa, a tear strength of 9kN·m ^-1 , an elongation at break of 120%, and a solid content of 60%.

Example 3

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight: 40 parts of polycaprolactone diol (molecular weight 2000), 80 parts of hexamethylene diisocyanate, chain extender methacrylic acid shrinkage 20 parts of glyceride, 0.04 parts of dibutyltin dilaurate as a catalyst, and 40 parts of N,N-dimethylformamide as a solvent.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of polycaprolactone diol (molecular weight 2000) (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours), and the dehydration treatment is obtained. polymer;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dibutyltin dilaurate and organic solvent N to the dehydrated polymer in step (1) at 80°C , N-dimethylformamide, stirring evenly, adding hexamethylene diisocyanate, reacting for 3h, to obtain a prepolymer;

(3) Add chain extender glycidyl methacrylate to the prepolymer in step (2), and react at 80° C. for 7 hours to obtain polyurethane adhesive.

The obtained polyurethane adhesive has a number average molecular weight of 22000, a transparency of 65%, a tensile strength of 4MPa, a tear strength of 10kN·m ^-1 , an elongation at break of 140%, and a solid content of 65%.

Example 4

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight:

40 parts of polycaprolactone diol (molecular weight 4000), 50 parts of xylylene diisocyanate, 10 parts of chain extender glycidyl etheroxypropyl trimethoxysilane, 0.04 part of catalyst dibutyltin dilaurate, solvent 40 parts of N,N-dimethylformamide.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of polycaprolactone diol (molecular weight 4000) (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours), and the dehydration treatment is obtained. polymer;

(2) Under the conditions of feeding inert gas (nitrogen) and stirring (stirring speed is 800r/min), add the catalyst glycidyl etheroxypropyl trimethoxy to the dehydrated polymer in step (1) at 80°C Silane and organic solvent N,N-dimethylformamide are stirred evenly, xylylene diisocyanate is added, and reacted for 4 hours to obtain a prepolymer;

(3) Add chain extender glycidyl etheroxypropyl trimethoxysilane to the prepolymer in step (2), and react at 80° C. for 6 hours to obtain a polyurethane adhesive.

The obtained polyurethane adhesive had a number average molecular weight of 20,000, a transparency of 70%, a tensile strength of 3.5 MPa, a tear strength of 10 kN·m ^-1 , an elongation at break of 130%, and a solid content of 65%.

Example 5

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight:

20 parts of succinic acid polyester diol (molecular weight 2000), 40 parts of dimethylmethane diisocyanate, 20 parts of chain extender glycidyl methacrylate, 0.04 part of catalyst dibutyltin dilaurate, solvent N,N-di 40 parts of methyl formamide.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of succinic acid polyester diol (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours) to obtain a dehydrated polymer;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dibutyltin dilaurate, organic solvent N to the dehydrated polymer of step (1) at 80°C , Stir N-dimethylformamide evenly, add dimethylmethane diisocyanate, react for 4 hours, and prepare a prepolymer;

(3) Add chain extender glycidyl methacrylate to the prepolymer in step (2), and react at 80°C for 6 hours to obtain polyurethane adhesive.

The obtained polyurethane adhesive has a number average molecular weight of 16000, a transparency of 60%, a tensile strength of 3.3MPa, a tear strength of 11kN·m ^-1 , an elongation at break of 130%, and a solid content of 60%.

Example 6

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight:

40 parts of succinic acid polyester diol (molecular weight 1000), 50 parts of hexamethylene diisocyanate, 10 parts of chain extender 1,4-butanediol, 0.04 parts of catalyst dimethylcyclohexylamine, solvent N, N - 40 parts of dimethylformamide.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Succinic acid polyester diol (molecular weight 1000) is subjected to dehydration treatment (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours), and the dehydration treatment is obtained. polymer;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dimethylcyclohexylamine and organic solvent to the dehydrated polymer in step (1) at 80°C N,N-dimethylformamide, stirred evenly, added hexamethylene diisocyanate, reacted for 3 hours, and obtained a prepolymer;

(3) Add chain extender 1,4-butanediol to the prepolymer in step (2), and react at 80° C. for 7 hours to obtain a polyurethane adhesive.

The obtained polyurethane adhesive has a number average molecular weight of 20000, a transparency of 75%, a tensile strength of 3.9MPa, a tear strength of 9kN·m ^-1 , a breaking elongation of 120%, and a solid content of 65%.

Example 7

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight:

Polypropylene oxide (molecular weight 2000) 20 parts, toluene diisocyanate 40 parts, chain extender glycidyl methacrylate 20 parts, catalyst dimethylcyclohexylamine 0.04 parts, solvent N,N-dimethylformamide 40 parts share.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of polypropylene oxide (molecular weight 2000) (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours), and the dehydration polymer is obtained;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dimethylcyclohexylamine and organic solvent to the dehydrated polymer in step (1) at 80°C N,N-dimethylformamide, stirred evenly, added toluene diisocyanate, reacted for 4 hours, and obtained a prepolymer;

(3) Add chain extender glycidyl methacrylate to the prepolymer in step (2), and react at 80°C for 6 hours to obtain polyurethane adhesive.

The obtained polyurethane adhesive has a number average molecular weight of 24,000, a transparency of 60%, a tensile strength of 4.5 MPa, a tear strength of 11kN·m ^-1 , an elongation at break of 120%, and a solid content of 65%.

Example 8

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight:

20 parts of polypropylene oxide (molecular weight 4000), 40 parts of hexamethylene diisocyanate, 20 parts of chain extender glycidyl methacrylate, 0.04 parts of catalyst dimethylcyclohexylamine, solvent N,N-dimethyl Formamide 40 parts.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of polypropylene oxide (molecular weight 4000) (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours), and the dehydration polymer is obtained;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dimethylcyclohexylamine and organic solvent to the dehydrated polymer in step (1) at 80°C N,N-dimethylformamide, stirred evenly, added hexamethylene diisocyanate, reacted for 4 hours, and obtained a prepolymer;

(3) Add chain extender glycidyl methacrylate to the prepolymer in step (2), and react at 80°C for 6 hours to obtain polyurethane adhesive.

The obtained polyurethane adhesive had a number average molecular weight of 26,000, a transparency of 55%, a tensile strength of 4.5 MPa, a tear strength of 10 kN·m ^-1 , an elongation at break of 110%, and a solid content of 65%.

Example 9

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight:

80 parts of polyoxypropylene ether diol (molecular weight 2000), 100 parts of hexamethylene diisocyanate, 20 parts of chain extender glycidyl etheroxypropyltrimethoxysilane, 0.05 part of catalyst dimethylcyclohexylamine, solvent 40 parts of N,N-dimethylformamide.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of polyoxypropylene ether glycol (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours), to obtain a dehydrated polymer;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dimethylcyclohexylamine and organic solvent to the dehydrated polymer in step (1) at 80°C N,N-dimethylformamide, stirred evenly, added hexamethylene diisocyanate, reacted for 4 hours, and obtained a prepolymer;

(3) Add chain extender glycidyl etheroxypropyl trimethoxysilane to the prepolymer in step (2), and react at 80° C. for 6 hours to obtain a polyurethane adhesive.

The obtained polyurethane adhesive has a number average molecular weight of 20,000, a transparency of 68%, a tensile strength of 4MPa, a tear strength of 11kN·m ^-1 , an elongation at break of 140%, and a solid content of 65%.

Example 10

A medical transparent high-strength polyurethane adhesive is prepared from the following raw materials in parts by weight:

Polyoxypropylene ether diol (molecular weight 1000) 60 parts, dimethylmethane diisocyanate 80 parts, chain extender glycidyl ether oxypropyl trimethoxysilane 20 parts, catalyst dibutyltin dilaurate 0.04 parts, solvent N , 40 parts of N-dimethylformamide.

The preparation method of described medical transparent high-strength polyurethane adhesive comprises the following steps:

(1) Dehydration treatment of polyoxypropylene ether glycol (molecular weight 1000) (the conditions of dehydration treatment are that the stirring rate is 1000r/min, the temperature is 110°C, the vacuum degree is 0.1Mpa, and the dehydration treatment is 2 hours), and the dehydration treatment is obtained. polymer;

(2) Under the condition of feeding inert gas (nitrogen) and stirring (the rotating speed of stirring is 800r/min), add catalyst dibutyltin dilaurate and organic solvent N to the dehydrated polymer in step (1) at 80°C , N-dimethylformamide, stirring evenly, adding dimethylmethane diisocyanate, reacting for 4h, to obtain a prepolymer;

(3) Add chain extender glycidyl etheroxypropyl trimethoxysilane to the prepolymer in step (2), and react at 80° C. for 6 hours to obtain a polyurethane adhesive.

The obtained polyurethane adhesive has a number average molecular weight of 16000, a transparency of 75%, a tensile strength of 3MPa, a tear strength of 9kN·m ^-1 , an elongation at break of 140%, and a solid content of 65%.

Claims (5)

1. A medical transparent high-strength polyurethane adhesive, characterized in that: it is prepared from the following raw materials in parts by weight: The polyester diol or polyether diol is more than one of polycaprolactone diol, polyoxypropylene ether diol or succinic acid polyester diol: the polyester diol Or the number average molecular weight of the polyether diol is 1000-5000; The diisocyanate is more than one of toluene diisocyanate, hexamethylene diisocyanate, dimethylmethane diisocyanate or xylylene diisocyanate; The chain extender is one or more of γ-glycidyl etheroxypropyl trimethoxysilane or glycidyl methacrylate. 2. The medical transparent high-strength polyurethane adhesive according to claim 1, characterized in that: the catalyst is one or more of stannous octoate, dibutyltin dilaurate or dimethylcyclohexylamine; The organic solvent is at least one of N,N-dimethylformamide, benzene, xylene or cyclohexanone. 3. According to the preparation method of the medical transparent high-strength polyurethane adhesive according to any one of claims 1 to 2, it is characterized in that: it specifically comprises the following steps: (1) dehydrating polyester diol or polyether diol to obtain a dehydrated polymer; (2) Add catalyst, organic solvent and diisocyanate to the dehydrated polymer in step (1) under the condition of feeding inert gas and stirring, and react at 60-80° C. for 3-4 hours to obtain a prepolymer; (3) Adding a chain extender to the prepolymer in step (2), reacting at 60-80° C. for 6-7 hours to obtain a polyurethane adhesive. 4. The preparation method of the medical transparent high-strength polyurethane adhesive according to claim 3, characterized in that: the conditions of the dehydration treatment in step (1) are that the stirring speed is 800～1200r/min, and the temperature is 105～115 ℃, the degree of vacuum is 0.08-0.16Mpa, and the dehydration treatment is 1-3 hours. 5. The method for preparing the medical transparent high-strength polyurethane adhesive according to claim 3, characterized in that: the stirring speed in step (2) is 600-800 r/min; the inert gas is nitrogen.