CN101928529B - EVA composite emulsion type low-temperature-resistant environment-friendly all-purpose adhesive and preparation method thereof - Google Patents

Abstract

The invention discloses an EVA composite emulsion type low temperature resistant environment-friendly universal adhesive and a preparation method thereof, belonging to the field of water-based adhesives, and the technical scheme is that the EVA emulsion is modified by rosin tackifying resin emulsion and polyurethane emulsion together to prepare the EVA emulsion type universal adhesive, wherein the EVA emulsion type universal adhesive comprises the following raw materials in parts by weight: 65-80 parts of EVA emulsion, 5-15 parts of rosin tackifying resin emulsion, 5-15 parts of polyurethane emulsion and the balance of auxiliaries, wherein the auxiliaries comprise an antifreezing agent, a plasticizer, a mildew preventive, a wetting agent and a pH regulator. When in preparation, the EVA emulsion is added into a dispersion kettle with a stirrer and stirred at a constant speed; adding the polyurethane emulsion, stirring and mixing for 1.0-1.5 hours; adding the rosin tackifying resin emulsion, the plasticizer dibutyl phthalate, the antifreezing agent ethylene glycol, the mildew preventive Kathon and the wetting agent, and stirring and mixing uniformly; adding pH regulator such as ammonia water or triethylamine, adjusting pH to 4.5-5.5, filtering and discharging. The obtained all-purpose adhesive has various indexes reaching or exceeding those of common white latex, is convenient to use, has wide application range, can be widely used for building decoration, furniture manufacture, bags and the like, can be used at normal temperature and can also be used at the low temperature of 5 ℃ to-5 ℃.

Description

EVA composite emulsion type low temperature resistant environmental protection universal adhesive and preparation method thereof

technical field

The invention relates to the technical field of universal glue and its preparation, in particular to the field of water-based adhesives.

Background technique

In the past, most of the all-purpose adhesives used in the construction and decoration industry were solvent-based neoprene adhesives. Not only the process is complicated, the cost is high, and the smell is strong, but also solvents such as benzene are used, which is harmful to human health. At present, the commercially available super glue also has solvent-based SBS super glue, which uses dichloromethane, dichloroethane, cyclohexane, solvent gasoline, etc. as solvents, causing air pollution and poison during use, and is flammable and explosive. . With the enhancement of people's awareness of environmental protection, the toxicity of adhesives and the negative impact on the environment have attracted increasing attention. Water-based adhesives have the advantages of environmental protection and little harm to human health, and have become the development direction of adhesives in the construction and decoration industry. However, the existing water-based adhesives still have problems such as low initial viscosity and low bonding strength, which limit their application range. In addition, the water-based adhesives currently on the market still contain organic solvents and are not truly environmentally friendly adhesives. Shanghai Tongbiao Quality Inspection Technology Co., Ltd. has selected 6 kinds of universal glue with good sales in the market: Panda 883 super glue, Zhengdian advanced universal glue, Oulong safety universal glue, Henkel Black & Decker universal glue, Jiangtian universal glue, Yonghe Super-grade universal glue, etc., the free formaldehyde content, benzene content, and total volatile organic compounds were tested. The test results are: the free formaldehyde content is 0.01g/kg~0.12g/kg, and the benzene content is 0.05g/kg~ 0.5g/kg, the total volatile organic compounds are 492g/L~678g/L.

EVA emulsion is formed by emulsion polymerization based on vinyl acetate and ethylene. Due to the introduction of ethylene, the discontinuity of the acetate group is formed, making the polymer main chain soft. The introduction of ethylene segments weakens the interaction within and between molecular chains and increases the mobility of molecular chains, thereby playing a role of "internal plasticization". This plasticizing effect is permanent, without the disadvantages of migration, volatilization, and exudation caused by small molecule plasticizers. Therefore, EVA emulsion has made great progress in production and application in recent years, but the molecular chain of ethylene-vinyl acetate copolymer lacks strong polar groups, so it is limited in some applications. EVA emulsion adhesives are not suitable for use below 5°C, which also limits their use in low temperature environments. In addition, the EVA emulsion has a large surface tension and poor wettability to the substrate, which is also an important reason for limiting the scope of use of EVA emulsion adhesives.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the existing EVA emulsion adhesive, and provide a kind of EVA emulsion type universal adhesive that does not contain organic solvents such as toluene and has excellent performance.

Another object of the present invention is to provide a method for preparing an EVA composite emulsion type low-temperature-resistant environmental protection universal adhesive with simple preparation process and easy implementation.

To achieve the above object, the present invention adopts the following technical solutions:

EVA composite emulsion type low temperature resistant environmental protection universal adhesive is characterized in that it is made of EVA emulsion jointly modified by rosin tackifying resin emulsion and polyurethane emulsion, and the ratio of raw materials in parts by weight is: EVA emulsion 65-80 parts, rosin 5-15 parts of tackifying resin emulsion, 5-15 parts of polyurethane emulsion, and the rest are auxiliary agents; the polyurethane emulsion is a combination of polyether polyurethane emulsion and crystalline polyester polyurethane emulsion, and is modified by nano- _SiO2. property; the polyether polyurethane emulsion comprises the following raw materials:

Toluene diisocyanate 14 parts

Polyether diol 90 parts

1,4-butanediol 1.5 parts

Trimethylolpropane 0.2 parts

Triethylamine 2.5 parts

Ethyl orthosilicate 2.3 parts

Dimethylolpropionic acid 3.5 parts

Ethylenediamine 0.5 parts

Proper amount of acetone

Water 200 parts

=4000）加入到带回流冷凝器和搅拌器的反应釜中，匀速搅拌，在85℃下反应3小时后；将反应降温至70℃左右，加入二羟甲基丙酸（DMPA）和少量辛酸亚锡（T-9），并同时加入少量丙酮；将反应温度控制在75℃，反应1.5小时；加入1,4-丁二醇（BDO）和三羟甲基丙烷（TMP），反应2小时后，降温出料；将其转移至乳化装置中，加入三乙胺（TEA），中和15分钟；再加入一定量的正硅酸乙酯（TEOS），搅拌10分钟后，向体系中加入适量蒸馏水，在高速搅拌下滴加稀释后的乙二胺（EDA），扩链反应15分钟，得到纳米SiO₂/聚氨酯复合乳液； The specific preparation method of polyether polyurethane emulsion is as follows: a certain proportion of toluene diisocyanate (TDI) and polyether diol (N240,

=4000) into the reaction kettle with reflux condenser and stirrer, stir at a constant speed, react at 85°C for 3 hours; cool the reaction to about 70°C, add dimethylolpropionic acid (DMPA) and a small amount of octanoic acid stannous (T-9), and at the same time add a small amount of acetone; control the reaction temperature at 75°C, react for 1.5 hours; add 1,4-butanediol (BDO) and trimethylolpropane (TMP), react for 2 hours Finally, cool down and discharge the material; transfer it to an emulsification device, add triethylamine (TEA), and neutralize for 15 minutes; then add a certain amount of tetraethyl orthosilicate (TEOS), stir for 10 minutes, and then add Appropriate amount of distilled water, add diluted ethylenediamine (EDA) dropwise under high-speed stirring, and perform chain extension reaction for 15 minutes to obtain nano-SiO ₂ /polyurethane composite emulsion;

Described polyester polyurethane emulsion comprises following raw material:

Toluene diisocyanate 29 parts

Polycarbonate diol 100 parts

1,4-butanediol 3.2 parts

Trimethylolpropane 0.3 parts

Triethylamine 3.3 parts

Ethyl orthosilicate 2.3 parts

Dimethylolpropionic acid 4.8 parts

Ethylenediamine 0.6 parts

Proper amount of acetone

Water 200 parts

The specific preparation method of polyester polyurethane emulsion is as follows: a certain proportion of toluene diisocyanate (TDI) and polycarbonate diol (PCDL, =2000) into the reaction kettle with reflux condenser and stirrer, stir at a constant speed, and react at 85°C for 2.5 hours; cool the reaction down to about 70°C, add dimethylolpropionic acid (DMPA) and a small amount of octanoic acid stannous (T-9), and a small amount of acetone was added at the same time; the reaction temperature was controlled at 75°C, and after 1.5 hours of reaction, 1,4-butanediol (BDO) and trimethylolpropane (TMP) were added, and the reaction was 2.0 Cool down and discharge after 1 hour; transfer it to an emulsification device, add triethylamine (TEA), neutralize for 15 minutes; then add a certain amount of tetraethyl orthosilicate (TEOS), stir for 10 minutes, then add Appropriate amount of distilled water was added dropwise with diluted ethylenediamine (EDA) under high-speed stirring, and the chain extension reaction was carried out for 15 minutes to obtain nano-SiO ₂ /polyurethane composite emulsion.

In order to achieve the above object, the present invention can also adopt the following technical solutions:

EVA composite emulsion type low temperature resistant environmental protection universal adhesive is characterized in that it is made of EVA emulsion jointly modified by rosin tackifying resin emulsion and polyurethane emulsion, and the ratio of raw materials in parts by weight is: EVA emulsion 65-80 parts, rosin 5-15 parts of tackifying resin emulsion, 5-15 parts of polyurethane emulsion, and the rest are auxiliary agents; the polyurethane emulsion is a combination of polyether polyurethane emulsion and crystalline polyester polyurethane emulsion, and is modified by nano- _SiO2. property; the polyether polyurethane emulsion comprises the following raw materials:

Toluene diisocyanate 23.5 parts

Polyether diol 85 parts

1,4-butanediol 3.5 parts

Trimethylolpropane 0.3 parts

Triethylamine 2.7 parts

Ethyl orthosilicate 2.3 parts

Dimethylolpropionic acid 3.6 parts

Proper amount of acetone

Ethylenediamine 0.7 parts

Water 200 parts

=2000）加入到带回流冷凝器和搅拌器的反应釜中，匀速搅拌，在85℃下反应2.5小时后；将反应降温至70℃左右，加入二羟甲基丙酸（DMPA）和少量辛酸亚锡（T-9），并同时加入少量丙酮；将反应温度控制在75℃，反应1.5小时后，加入1,4-丁二醇（BDO）和三羟甲基丙烷（TMP），反应2.0小时后降温出料；将其转移至乳化装置中，加入三乙胺（TEA），中和15分钟；再加入一定量的正硅酸乙酯（TEOS），搅拌10分钟后，向体系中加入适量蒸馏水，在高速搅拌下滴加稀释后的乙二胺（EDA），扩链反应20分钟，得到纳米SiO₂/聚氨酯复合乳液； The specific preparation method of polyether polyurethane emulsion is as follows: a certain proportion of toluene diisocyanate (TDI) and polyether diol (N220,

=2000) into the reaction kettle with reflux condenser and stirrer, stir at a constant speed, and react at 85°C for 2.5 hours; cool the reaction down to about 70°C, add dimethylolpropionic acid (DMPA) and a small amount of octanoic acid stannous (T-9), and a small amount of acetone was added at the same time; the reaction temperature was controlled at 75°C, and after 1.5 hours of reaction, 1,4-butanediol (BDO) and trimethylolpropane (TMP) were added, and the reaction was 2.0 Cool down and discharge after 1 hour; transfer it to an emulsification device, add triethylamine (TEA), neutralize for 15 minutes; then add a certain amount of tetraethyl orthosilicate (TEOS), stir for 10 minutes, then add Appropriate amount of distilled water, add diluted ethylenediamine (EDA) dropwise under high-speed stirring, and perform chain extension reaction for 20 minutes to obtain nano-SiO ₂ /polyurethane composite emulsion;

Described polyester polyurethane emulsion comprises following raw material:

Toluene diisocyanate 29 parts

Polycarbonate diol 100 parts

1,4-butanediol 3.2 parts

Trimethylolpropane 0.3 parts

Triethylamine 3.3 parts

Ethyl orthosilicate 2.3 parts

Dimethylolpropionic acid 4.8 parts

Ethylenediamine 0.6 parts

Proper amount of acetone

Water 200 parts

=2000）加入到带回流冷凝器和搅拌器的反应釜中，匀速搅拌，在85℃下反应2.5小时后；将反应降温至70℃左右，加入二羟甲基丙酸（DMPA）和少量辛酸亚锡（T-9），并同时加入少量丙酮；将反应温度控制在75℃，反应1.5小时后，加入1,4-丁二醇（BDO）和三羟甲基丙烷（TMP），反应2.0小时后降温出料；将其转移至乳化装置中，加入三乙胺（TEA），中和15分钟；再加入一定量的正硅酸乙酯（TEOS），搅拌10分钟后，向体系中加入适量蒸馏水，在高速搅拌下滴加稀释后的乙二胺（EDA），扩链反应15分钟，得到纳米SiO₂/聚氨酯复合乳液。 The specific preparation method of polyester polyurethane emulsion is as follows: a certain proportion of toluene diisocyanate (TDI) and polycarbonate diol (PCDL,

=2000) into the reaction kettle with reflux condenser and stirrer, stir at a constant speed, and react at 85°C for 2.5 hours; cool the reaction down to about 70°C, add dimethylolpropionic acid (DMPA) and a small amount of octanoic acid stannous (T-9), and a small amount of acetone was added at the same time; the reaction temperature was controlled at 75°C, and after 1.5 hours of reaction, 1,4-butanediol (BDO) and trimethylolpropane (TMP) were added, and the reaction was 2.0 Cool down and discharge after 1 hour; transfer it to an emulsification device, add triethylamine (TEA), neutralize for 15 minutes; then add a certain amount of tetraethyl orthosilicate (TEOS), stir for 10 minutes, then add Appropriate amount of distilled water was added dropwise with diluted ethylenediamine (EDA) under high-speed stirring, and the chain extension reaction was carried out for 15 minutes to obtain nano-SiO ₂ /polyurethane composite emulsion.

The auxiliary agent includes antifreezing agent, plasticizer, antifungal agent, wetting agent and pH regulator.

The pH regulator is ammonia water or triethylamine to adjust the pH of the emulsion to 4.5-5.5.

The antifreezing agent is ethylene glycol, and the parts by weight are 1-2 parts.

The plasticizer is dibutyl phthalate, and the proportion by weight is 0-3 parts.

The antifungal agent is Kasone, and the parts by weight are 2 parts.

A preparation method of EVA composite emulsion type low temperature resistant environmental protection universal adhesive, characterized in that: comprising the following steps:

1) Add the EVA emulsion into the dispersing kettle with a stirrer and stir at a constant speed;

2) Add polyurethane emulsion, stir and mix for 1.0-1.5 hours;

3) Then add rosin tackifying resin emulsion, plasticizer dibutyl phthalate, antifreeze agent ethylene glycol, antifungal agent Cathone, wetting agent, stir and mix evenly;

4) Add a pH regulator such as ammonia water or triethylamine to adjust the pH value to 4.5-5.5, and filter out the material.

The present invention has the following advantages:

1. Modification of EVA emulsion with polyurethane emulsion and rosin tackifying resin emulsion not only introduces strong polar groups, but also increases the affinity to the substrate, so that the application range of EVA emulsion adhesive is wider, and guarantees The adhesive performance of the EVA emulsion adhesive will not deteriorate below 5°C, thereby expanding the use temperature range of the EVA emulsion adhesive. Rosin tackifying resin emulsion does not contain organic solvents such as toluene, and truly meets the requirements of environmental protection and harmlessness to human health.

2. The polyurethane emulsion is modified with nano- _SiO2 , which improves the final bonding strength of EVA glue and makes the film have better water and weather resistance. The hydroxyl groups on the surface of inorganic nanoparticles can interact with the polar groups on the polymer chain in the form of hydrogen bonds or chemical bonds to form internal crosslinks, improve the adhesive strength, and improve the heat resistance of the adhesive. In addition, the addition of nanoparticles can not only improve the fluidity and sizing and brushing properties of the adhesive, make the adhesive evenly coated, reduce the amount of glue applied, but also increase the force between the adhesive and the surface of the adherend, so that both closely combined.

3. Polyurethane has strong polar groups and high activity, and has good affinity for many substrates, thereby broadening the application range of the product. The prepared EVA composite emulsion type universal adhesive has a wide range of applications and can be used in Architectural decoration, furniture production and bags, etc., can be used not only at room temperature, but also at low temperatures of 5°C to -5°C.

4. The preparation process is simple, easy to implement, and low in cost. The preparation process will not pollute and poison the air, has excellent environmental protection, improves the working environment and effectively protects human health.

Detailed ways:

The invention not only provides an EVA composite emulsion type low-temperature-resistant environmental protection universal adhesive, which is prepared by jointly modifying the EVA emulsion with rosin tackifying resin emulsion and polyurethane emulsion, but also provides a matching preparation method.

The present invention will be further described below in conjunction with embodiment.

Example 1

The preparation of polyether type polyurethane emulsion comprises the following raw materials:

Toluene diisocyanate 14 parts

Polyether diol 90 parts

1,4-butanediol 1.5 parts

Trimethylolpropane 0.2 parts

Triethylamine 2.5 parts

Ethyl orthosilicate 2.3 parts

Dimethylolpropionic acid 3.5 parts

Ethylenediamine 0.5 parts

Proper amount of acetone

Water 200 parts

The specific preparation method is as follows:

=4000）加入到带回流冷凝器和搅拌器的反应釜中，匀速搅拌，在85℃下反应3小时后。将反应降温至70℃左右，加入二羟甲基丙酸（DMPA）和少量辛酸亚锡（T-9），并同时加入少量丙酮。将反应温度控制在75℃，反应1.5小时；加入1,4-丁二醇（BDO）和三羟甲基丙烷（TMP），反应2小时后，降温出料。将其转移至乳化装置中，加入三乙胺（TEA），中和15分钟。再加入一定量的正硅酸乙酯（TEOS），搅拌10分钟后，向体系中加入适量蒸馏水，在高速搅拌下滴加稀释后的乙二胺（EDA），扩链反应15分钟，得到纳米SiO₂/聚氨酯复合乳液。 A certain proportion of toluene diisocyanate (TDI) and polyether diol (N240,

=4000) into a reaction kettle with a reflux condenser and a stirrer, stirred at a constant speed, and reacted at 85°C for 3 hours. Cool the reaction down to about 70°C, add dimethylolpropionic acid (DMPA) and a small amount of stannous octoate (T-9), and add a small amount of acetone at the same time. Control the reaction temperature at 75°C, react for 1.5 hours; add 1,4-butanediol (BDO) and trimethylolpropane (TMP), react for 2 hours, cool down and discharge. Transfer it to an emulsification device, add triethylamine (TEA), and neutralize for 15 minutes. Then add a certain amount of tetraethyl orthosilicate (TEOS), stir for 10 minutes, add an appropriate amount of distilled water to the system, add diluted ethylenediamine (EDA) dropwise under high-speed stirring, and perform a chain extension reaction for 15 minutes to obtain nano SiO ₂ /polyurethane composite emulsion.

The preparation of polyester polyurethane emulsion comprises the following raw materials:

Toluene diisocyanate 29 parts

Polycarbonate diol 100 parts

1,4-butanediol 3.2 parts

Trimethylolpropane 0.3 parts

Triethylamine 3.3 parts

Ethyl orthosilicate 2.3 parts

Dimethylolpropionic acid 4.8 parts

Ethylenediamine 0.6 parts

Proper amount of acetone

Water 200 parts

The specific preparation method is as follows:

=2000）加入到带回流冷凝器和搅拌器的反应釜中，匀速搅拌，在85℃下反应2.5小时后。将反应降温至70℃左右，加入二羟甲基丙酸（DMPA）和少量辛酸亚锡（T-9），并同时加入少量丙酮。将反应温度控制在75℃，反应1.5小时后，加入1,4-丁二醇（BDO）和三羟甲基丙烷（TMP），反应2.0小时后降温出料。将其转移至乳化装置中，加入三乙胺（TEA），中和15分钟。再加入一定量的正硅酸乙酯（TEOS），搅拌10分钟后，向体系中加入适量蒸馏水，在高速搅拌下滴加稀释后的乙二胺（EDA），扩链反应15分钟，得到纳米SiO₂/聚氨酯复合乳液。 A certain proportion of toluene diisocyanate (TDI) and polycarbonate diol (PCDL,

=2000) into a reaction kettle with a reflux condenser and a stirrer, stirred at a constant speed, and reacted at 85°C for 2.5 hours. Cool the reaction down to about 70°C, add dimethylolpropionic acid (DMPA) and a small amount of stannous octoate (T-9), and add a small amount of acetone at the same time. The reaction temperature was controlled at 75°C. After 1.5 hours of reaction, 1,4-butanediol (BDO) and trimethylolpropane (TMP) were added, and the temperature was lowered after 2.0 hours of reaction. Transfer it to an emulsification device, add triethylamine (TEA), and neutralize for 15 minutes. Then add a certain amount of tetraethyl orthosilicate (TEOS), stir for 10 minutes, add an appropriate amount of distilled water to the system, add diluted ethylenediamine (EDA) dropwise under high-speed stirring, and perform a chain extension reaction for 15 minutes to obtain nano SiO ₂ /polyurethane composite emulsion.

The preparation of EVA emulsion type universal adhesive comprises the following raw materials:

EVA lotion 75 servings

Rosin tackifying resin emulsion 15 parts

Polyether polyurethane emulsion 5 parts

Ethylene glycol 1 part

Dibutyl phthalate 1 part

Casson 2 servings

Wetting agent 0.5 parts

pH adjuster Appropriate amount

The specific preparation method is as follows:

Add the EVA emulsion to the dispersing tank with agitator, stir at a constant speed, add polyether polyurethane emulsion, stir for 1.0 hour, then add rosin tackifying resin emulsion, plasticizer dibutyl phthalate (DBP), antifreeze Agent ethylene glycol, antifungal agent Kathon, wetting agent, stir and mix evenly, add pH regulator ammonia water, adjust the pH value to 4.5, filter and discharge.

Example 2

Prepare polyether type polyurethane emulsion raw material and specific method with embodiment 1.

Preparation of polyester polyurethane emulsion raw materials and specific methods are the same as in Example 1.

The preparation of EVA emulsion type universal adhesive comprises the following raw materials:

EVA lotion 80 parts

Rosin tackifying resin emulsion 10 parts

Polyester polyurethane emulsion 5 parts

Ethylene glycol 1 part

Dibutyl phthalate 0.5 parts

Casson 2 servings

Wetting agent 0.6 parts

pH adjuster Appropriate amount

The specific preparation method is the same as in Example 1, and will not be repeated here.

Example 3

Prepare polyether type polyurethane emulsion raw material and specific method with embodiment 1.

Preparation of polyester polyurethane emulsion raw materials and specific methods are the same as in Example 1.

The preparation of EVA emulsion type universal adhesive comprises the following raw materials:

EVA lotion 70 parts

Rosin tackifying resin emulsion 10 parts

Polyether polyurethane emulsion 10 parts

Polyester polyurethane emulsion 5 parts

Ethylene glycol 1 part

Dibutyl phthalate 0.5 parts

Casson 2 servings

Wetting agent 0.6 parts

pH adjuster Appropriate amount

The specific preparation method is the same as in Example 1, and will not be repeated here.

Example 4

Prepare polyether type polyurethane emulsion raw material and specific method with embodiment 1.

Preparation of polyester polyurethane emulsion raw materials and specific methods are the same as in Example 1.

The preparation of EVA emulsion type universal adhesive comprises the following raw materials:

EVA lotion 75 parts

Rosin tackifying resin emulsion 10 parts

Polyether polyurethane emulsion 5 parts

Polyester polyurethane emulsion 5 parts

Ethylene glycol 1 part

Dibutyl phthalate 1 part

Casson 2 servings

Wetting agent 0.7 parts

pH adjuster Appropriate amount

The specific preparation method is as follows:

Add the EVA emulsion to the dispersing tank with a stirrer, stir at a constant speed, add the polyurethane emulsion, stir for 1.5 hours, then add the rosin tackifying resin emulsion, antifreeze agent ethylene glycol, plasticizer dibutyl phthalate (DBP ), antifungal agent Casson and wetting agent, stir and mix evenly, add pH regulator triethylamine, adjust the pH value to 5.5, and filter out the material.

Example 5

The preparation of polyether type polyurethane emulsion comprises the following raw materials:

Toluene diisocyanate 23.5 parts

Polyether diol 85 parts

1,4-butanediol 3.5 parts

Trimethylolpropane 0.3 parts

Triethylamine 2.7 parts

Ethyl orthosilicate 2.3 parts

Dimethylolpropionic acid 3.6 parts

Proper amount of acetone

Ethylenediamine 0.7 parts

Water 200 parts

The specific preparation method is as follows:

A certain proportion of toluene diisocyanate (TDI) and polyether diol (N220, =2000) into a reaction kettle with a reflux condenser and a stirrer, stirred at a constant speed, and reacted at 85°C for 2.5 hours. Cool the reaction down to about 70°C, add dimethylolpropionic acid (DMPA) and a small amount of stannous octoate (T-9), and add a small amount of acetone at the same time. The reaction temperature was controlled at 75°C. After 1.5 hours of reaction, 1,4-butanediol (BDO) and trimethylolpropane (TMP) were added, and the temperature was lowered after 2.0 hours of reaction. Transfer it to an emulsification device, add triethylamine (TEA), and neutralize for 15 minutes. Then add a certain amount of tetraethyl orthosilicate (TEOS), stir for 10 minutes, add an appropriate amount of distilled water to the system, add diluted ethylenediamine (EDA) dropwise under high-speed stirring, and perform a chain extension reaction for 20 minutes to obtain nano SiO ₂ /polyurethane composite emulsion.

Preparation of polyester polyurethane emulsion raw materials and specific methods are the same as in Example 1.

The preparation of EVA emulsion type universal adhesive comprises the following raw materials:

EVA lotion 65 parts

Rosin lotion 10 parts

Polyether polyurethane emulsion 10 parts

Polyester polyurethane emulsion 5 parts

Ethylene glycol 2 parts

Dibutyl phthalate 3 parts

Casson 2 servings

Wetting agent 2 parts

pH adjuster Appropriate amount

The specific preparation method is the same as in Example 1, and will not be repeated here.

The EVA super glue related performance test results of Examples 1-5 are shown in Table 1.

Table 1 Basic properties of EVA emulsion type universal adhesive

Claims (1)

1.EVA the low temperature resistant environmentally-friendly universal glue of composite emulsion type, it is characterized in that: it is to be made by rosin tackifier resin emulsion and the common modified EVA emulsion of polyaminoester emulsion, the raw materials by weight portion proportioning is: EVA emulsion 65-80 part, rosin tackifier resin emulsion 5-15 part, polyaminoester emulsion 5-15 part, all the other are auxiliary agent; Described polyaminoester emulsion is the combination of polyether(poly)urethane emulsion, crystalline polyester type polyurethane emulsion, and adopts nanometer SiO ₂Carried out modification; Described polyether(poly)urethane emulsion comprises following raw materials according:

14 parts of tolylene diisocyanates

90 parts of polyether Glycols

1.5 parts of BDOs

0.2 part of TriMethylolPropane(TMP)

2.5 parts of triethylamines

2.3 parts of tetraethoxys

3.5 parts of dimethylol propionic acids

0.5 part of quadrol

Acetone is appropriate

200 parts of distilled water

Concrete preparation method is as follows for the polyether(poly)urethane emulsion: a certain proportion of tolylene diisocyanate and polyether Glycols join in reactor with reflux exchanger and agitator, at the uniform velocity stir, in reaction under 85 ℃ after 3 hours; Reaction is cooled to 70 ℃, adds dimethylol propionic acid and a small amount of stannous octoate, and add simultaneously a small amount of acetone; Temperature of reaction is controlled at 75 ℃, reacted 1.5 hours; Add BDO and TriMethylolPropane(TMP), react after 2 hours cooling discharge; Transfer them in emulsifier unit, add triethylamine, in and 15 minutes; Add a certain amount of tetraethoxy again, stir after 10 minutes, add appropriate distilled water in system, drip the quadrol after diluting under high-speed stirring, chain extending reaction 15 minutes obtains nanometer SiO ₂/ urethane composite emulsion;

Described crystalline polyester type polyurethane emulsion comprises following raw materials according:

29 parts of tolylene diisocyanates

100 parts of PCDL

3.2 parts of BDOs

0.3 part of TriMethylolPropane(TMP)

3.3 parts of triethylamines

2.3 parts of tetraethoxys

4.8 parts of dimethylol propionic acids

0.6 part of quadrol

Acetone is appropriate

200 parts of distilled water

Concrete preparation method is as follows for crystalline polyester type polyurethane emulsion: a certain proportion of tolylene diisocyanate and PCDL join in reactor with reflux exchanger and agitator, at the uniform velocity stir, in reaction under 85 ℃ after 2.5 hours; Reaction is cooled to 70 ℃, adds dimethylol propionic acid and a small amount of stannous octoate, and add simultaneously proper amount of acetone; Temperature of reaction is controlled at 75 ℃, reacts after 1.5 hours, add BDO and TriMethylolPropane(TMP), react cooling discharge after 2.0 hours; Transfer them in emulsifier unit, add triethylamine, in and 15 minutes; Add a certain amount of tetraethoxy again, stir after 10 minutes, add appropriate distilled water in system, drip the quadrol after diluting under high-speed stirring, chain extending reaction 15 minutes obtains nanometer SiO ₂/ urethane composite emulsion.

2, the low temperature resistant environmentally-friendly universal glue of EVA composite emulsion type according to claim 1, it is characterized in that: described auxiliary agent comprises frostproofer, softening agent, mould inhibitor, wetting agent and pH value conditioning agent.

3, the low temperature resistant environmentally-friendly universal glue of EVA composite emulsion type according to claim 2, it is characterized in that: pH value conditioning agent is ammoniacal liquor or triethylamine, and the pH value of emulsion is transferred to 4.5-5.5.

4, the low temperature resistant environmentally-friendly universal glue of EVA composite emulsion type according to claim 2, it is characterized in that: described frostproofer is ethylene glycol.

5, the low temperature resistant environmentally-friendly universal glue of EVA composite emulsion type according to claim 2, it is characterized in that: described softening agent is dibutyl phthalate.

6, the low temperature resistant environmentally-friendly universal glue of EVA composite emulsion type according to claim 2, it is characterized in that: described mould inhibitor is Kathon CG.

7, the low temperature resistant environmentally-friendly universal glue of EVA composite emulsion type, it is characterized in that: it is to be made by rosin tackifier resin emulsion and the common modified EVA emulsion of polyaminoester emulsion, the raw materials by weight portion proportioning is: EVA emulsion 65-80 part, rosin tackifier resin emulsion 5-15 part, polyaminoester emulsion 5-15 part, all the other are auxiliary agent; Described polyaminoester emulsion is the combination of polyether(poly)urethane emulsion, crystalline polyester type polyurethane emulsion, and adopts nanometer SiO ₂Carried out modification; Described polyether(poly)urethane emulsion comprises following raw materials according:

23.5 parts of tolylene diisocyanates

85 parts of polyether Glycols

3.5 parts of BDOs

0.3 part of TriMethylolPropane(TMP)

2.7 parts of triethylamines

2.3 parts of tetraethoxys

3.6 parts of dimethylol propionic acids

Acetone is appropriate

0.7 part of quadrol

200 parts of distilled water

Concrete preparation method is as follows for the polyether(poly)urethane emulsion: a certain proportion of tolylene diisocyanate and polyether Glycols join in reactor with reflux exchanger and agitator, at the uniform velocity stir, in reaction under 85 ℃ after 2.5 hours; Reaction is cooled to 70 ℃, adds dimethylol propionic acid and a small amount of stannous octoate, and add simultaneously proper amount of acetone; Temperature of reaction is controlled at 75 ℃, reacts after 1.5 hours, add BDO and TriMethylolPropane(TMP), react cooling discharge after 2.0 hours; Transfer them in emulsifier unit, add triethylamine, in and 15 minutes; Add a certain amount of tetraethoxy again, stir after 10 minutes, add appropriate distilled water in system, drip the quadrol after diluting under high-speed stirring, chain extending reaction 20 minutes obtains nanometer SiO ₂/ urethane composite emulsion;

Described crystalline polyester type polyurethane emulsion comprises following raw materials according:

29 parts of tolylene diisocyanates

100 parts of PCDL

3.2 parts of BDOs

0.3 part of TriMethylolPropane(TMP)

3.3 parts of triethylamines

2.3 parts of tetraethoxys

4.8 parts of dimethylol propionic acids

0.6 part of quadrol

Acetone is appropriate

200 parts of distilled water

Concrete preparation method is as follows for crystalline polyester type polyurethane emulsion: a certain proportion of tolylene diisocyanate and PCDL join in reactor with reflux exchanger and agitator, at the uniform velocity stir, in reaction under 85 ℃ after 2.5 hours; Reaction is cooled to 70 ℃, adds dimethylol propionic acid and a small amount of stannous octoate, and add simultaneously proper amount of acetone; Temperature of reaction is controlled at 75 ℃, reacts after 1.5 hours, add BDO and TriMethylolPropane(TMP), react cooling discharge after 2.0 hours; Transfer them in emulsifier unit, add triethylamine, in and 15 minutes; Add a certain amount of tetraethoxy again, stir after 10 minutes, add appropriate distilled water in system, drip the quadrol after diluting under high-speed stirring, chain extending reaction 15 minutes obtains nanometer SiO ₂/ urethane composite emulsion.

8, the low temperature resistant environmentally-friendly universal glue of EVA composite emulsion type according to claim 7, it is characterized in that: described auxiliary agent comprises frostproofer, softening agent, mould inhibitor, wetting agent and pH value conditioning agent; Wherein, pH value conditioning agent is ammoniacal liquor or triethylamine, and the pH value of emulsion is transferred to 4.5-5.5; Described frostproofer is ethylene glycol; Described softening agent is dibutyl phthalate; Described mould inhibitor is Kathon CG.