CN105062402B - A kind of environmentally friendly sports field polyurethane glue and preparation method thereof - Google Patents

Abstract

A kind of environmentally friendly sports field polyurethane glue and preparation method thereof, glue is made up of PPG 30 ~ 60%, methyl diphenylene diisocyanate 5 ~ 15%, thermoplastic resin 5 ~ 10%, modified molecular screen 3 ~ 7%, auxiliary agent 10 ~ 25%, castor oil 3 ~ 10% and nanometer inorganic filler 5 ~ 10%, and inorganic filler is 1 by weight ratio：1.5 ~ 2 alumina powder and white carbon capsule of nano powder composition；Its preparation method improves production and construction environment, optimizes the hardening time of product, technological process is simple；Selection and proportioning of the present invention by above-mentioned raw materials, it is ensured that the organic coordination of soft or hard chain after glue shaping, can be good at carrying out molecules align between phase and phase, glue has good elongation, adds tensile strength.

Description

A kind of polyurethane glue for environment-friendly sports ground and preparation method thereof

technical field

The invention relates to the field of sports, in particular to an environmentally friendly polyurethane glue for sports venues and a preparation method thereof.

Background technique

In 1968, polyurethane adhesives were used for the bonding of glass fiber reinforced plastics. After the improvement of the two-component polyurethane packaging and the use of one-component polyurethane adhesives in 1978, the development of polyurethane adhesives was accelerated. With the development of our country's national fitness campaign, the use of polyurethane adhesives is showing a trend of vigorous development.

Polyurethane glue is a semi-finished product of organic synthesis calculated by the equivalent ratio of polyether and isocyanate. At present, in the actual use of most plastic runway glues, due to differences in the selection of raw materials, proportioning and synthesis processes when designing formulas, the mechanical properties and construction environment are relatively poor, and the traditionally used toluene diisocyanate (TDI ) type and MOCA (polyurethane rubber vulcanizing agent), due to the heavy metal substances contained in the TDI polyurethane track, it will oxidize and pollute the environment during use. For example, lead becomes lead oxide after oxidation, which affects human health in the form of dust. Lead mostly accumulates in the atmosphere about 1m above the ground, in the breathing zone of children, and has a greater impact on health. Free TDI can volatilize within a few years, but the toxic and harmful chemicals in the material will cause damage to the human body and cause adverse effects on the environment.

Contents of the invention

The purpose of the present invention is to provide a kind of polyurethane glue for environment-friendly sports venues and its preparation method, in order to overcome the harm and unsafeness to the human body caused by the difference in the synthesis process of the traditional polyurethane glue for sports venues and the raw materials used in the glue Hidden danger.

The technical scheme adopted by the present invention to achieve the above object is: a kind of polyurethane glue for environment-friendly sports venues, which is composed of polyether polyol, diphenylmethane diisocyanate, thermoplastic resin, modified molecular sieve, auxiliary agent, castor oil and inorganic filler Composition, the weight percentage of each component is as follows: polyether polyol 30~60%, diphenylmethane diisocyanate 5~15%, thermoplastic resin 5~10%, modified molecular sieve 3~7%, additive 10~ 25%, castor oil 3~10%, and nano inorganic filler 5~10%, wherein the inorganic filler is composed of alumina micropowder and white carbon black nano microcapsule powder with a weight ratio of 1:1.5~2.

Among them, polyether polyol is composed of polyether polyol main material and polyether polyol auxiliary material with a weight ratio of 2~5:1, and the main material of polyether polyol is polyoxypropylene glycerol ether with a molecular weight of 5000 -7000; the auxiliary material of polyether polyol is polyoxypropylene propylene glycol ether, the molecular weight is 1000-4000.

In the present invention, the thermoplastic resin is composed of tert-butylphenolic resin and terpene resin with a weight ratio of 1:1~2.

In the present invention, diphenylmethane diisocyanate is 4,4-diphenylmethane diisocyanate and/or 2,4-diphenylmethane diisocyanate.

In the present invention, the auxiliary agent is dioctyl phthalate.

In the present invention, the particle size of the alumina micropowder is 1-6 micrometers, and the purity is 98%; the particle size of the white carbon black nano-microcapsule powder is 20 nanometers, and the purity is >99.5%.

A preparation method of polyurethane glue for environment-friendly sports venues, comprising the following steps: step 1, according to the weight ratio of 1:3:3, take nano-microcapsule powder, nano-white carbon black and dehydrated alcohol, mix them in 40~ Ultrasonic disperse at a frequency of 50KHz for 20~25min, then perform suction filtration under a vacuum condition of 0.098MPa, stop the suction filtration when there are no more ethanol droplets dripping, take out the filtrate, put it in an oven, and Carry out drying at 30°C×6h and preheating at 50°C×20min, take out the preheated material, put it in a press and pre-press it at 2MPa for 5min, and then press it at 5MPa, 145~155°C Under hot pressing for 28-30min, after naturally cooling to room temperature, the white carbon black nanocapsule powder is prepared and set aside;

Step 2. Weigh sodium borate and molecular sieve according to the weight ratio of 2:100, dissolve all the sodium borate in deionized water, then add the weighed molecular sieve, and immerse in a water bath at 50°C for 6 hours to obtain a modified molecular sieve; boron Into the inorganic framework of the molecular sieve, the surface of the inorganic group is modified, and its adsorption performance is improved; wherein, the molecular sieve used in the present invention is a 13X type molecular sieve.

Step 3: According to the weight percentage, add polyether polyol into the reaction kettle, and stir at 70~85°C for 0.5~1h, then carry out vacuum degassing and dehydration treatment for 1~2.5h, then cool it down To 40 ~ 60 ℃, standby;

Step 4. On the basis of step 3, add the diphenylmethane diisocyanate in the weight percentage, react at 70-90°C for 2.5h, and cool to 40-60°C for later use;

Step 5. According to the weight ratio of 1:1.5~2, respectively weigh the alumina micropowder and the white carbon black nano-microcapsule powder prepared in step 1, and mix them to obtain inorganic fillers; Inorganic fillers, thermoplastic resins, additives, castor oil and the modified molecular sieve prepared in step 2 are stirred for 0.5-1 hour to obtain a mixed solution, and the mixed solution is discharged under the protection of a nitrogen atmosphere to obtain polyurethane glue.

The preparation method improves the production and construction environment, and optimizes the curing time of the product; the process flow is simple, the operation is convenient, and the construction efficiency and construction quality are guaranteed; the raw materials used overcome the harm to the human body caused by the traditional use of TDI and MOCA And unsafe hidden dangers, environmental protection, no pollution, environmental protection, low production cost.

In the present invention, the high fluidity and nano-size effect of the white carbon black nano-microcapsule powder greatly enhance the wear resistance of the glue. The surface active points of white carbon black nano-microcapsule powder and the chemical adsorption of surface functional groups can avoid the passivation of glue.

Beneficial effects: (1) In the polyurethane glue system of the present invention, adding a certain amount of tert-butylphenolic resin can increase the peel strength of the system; adding a certain amount of terpene resin can not only improve the bonding strength of the system to materials, Moreover, it can improve the heat resistance of the glue; the added inorganic filler has small particle size, large specific surface area, and high surface hydroxyl content. Due to the nano-effect provided by its size, it has high surface energy and can improve the glue. Shear strength and peel strength. Among them, the nano-microencapsulation of white carbon black enables it to disperse in the glue system, has a balance effect of stress concentration, can absorb the impact of the glue, and reduces the shrinkage and deformation of the glue;

(2) Further, the modified molecular sieve has a strong affinity for water and carbon dioxide, which can absorb trace moisture in the glue, reduce moisture, and reduce the generation of carbon dioxide; prolong the service life of polyurethane glue, and can also eliminate the curing of polyurethane glue The resulting air bubbles avoid bubbling on the bonding surface and improve the bonding strength of the polyurethane glue; at the same time, the modified molecular sieve is used as a filler to reduce production costs.

(3) The molecular structure of castor oil contains hydroxyl groups and a large number of double bonds, which can increase the cross-linking point of the reaction, increase the cross-linking density, transform the material from a linear structure to a body-shaped structure, and increase the cohesive energy of the molecule. The intermolecular combination is stronger, which limits the movement and rotation of chain segments and groups, and improves the shear strength and tear-off strength of the glue; moreover, the long-chain non-polar fatty acids contained in castor oil make the glue have good Hydrolysis resistance and flexibility.

(4), the present invention ensures the organic coordination of soft and hard chains after the glue is formed through the selection and proportioning of the above raw materials, and the molecular arrangement between phases can be well carried out. The glue has good elongation and increases Tensile Strength.

detailed description

The polyurethane glue for environment-friendly sports venues of the present invention and its preparation method will be further described below in conjunction with specific examples, so that those skilled in the art can better understand the present invention and can implement it, but the examples given are not intended as a reference to the present invention. limit.

An environmentally friendly polyurethane glue for sports venues, consisting of polyether polyol, diphenylmethane diisocyanate, thermoplastic resin, modified molecular sieve, additives, castor oil and inorganic fillers, the weight percentage of each component is as follows: polyether Polyol 30~60%, diphenylmethane diisocyanate 5~15%, thermoplastic resin 5~10%, modified molecular sieve 3~7%, additive 10~25%, castor oil 3~10% and nano inorganic filler 5~10%, wherein the inorganic filler is composed of alumina micropowder and white carbon black nano-capsule powder with a weight ratio of 1:1.5~2.

Example 1:

A preparation method of polyurethane glue for environment-friendly sports venues, comprising the following steps: Step 1, according to the weight ratio of 1:3:3, weigh nano-microcapsule powder, nano-silica and absolute ethanol, mix them at 45KHz Ultrasonic dispersion at high frequency for 23 minutes, and then carry out suction filtration under the vacuum condition of 0.098MPa, stop the suction filtration when there are no more ethanol droplets dripping, take out the filtrate, put it in an oven, and carry out 30°C× After drying for 6 hours and preheating at 50°C×20min, take out the preheated material, put it in a press, pre-press it at 2MPa for 5min, and then press at 5MPa and 145°C for 30min, naturally After being cooled to room temperature, white carbon black nanocapsule powder was prepared, which was set aside;

Step 2. Weigh sodium borate and molecular sieve according to the weight ratio of 2:100, dissolve all the sodium borate in deionized water, then add the weighed molecular sieve, and immerse in a water bath at 50°C for 6 hours to obtain a modified molecular sieve;

Step 3: According to the weight percentage, add polyether polyol into the reaction kettle, and stir at 85°C for 0.5~1h, then carry out vacuum degassing and dehydration treatment for 1.5h, then cool it to 45°C, spare;

Step 4. On the basis of step 3, add the diphenylmethane diisocyanate in the weight percentage, react at 90°C for 2.5h, and cool to 45°C for later use;

Step 5, according to weight percentage, take by weighing 40% polyoxypropylene glycerol ether, 20% polyoxypropylene propylene glycol ether, 5% 4,4-diphenylmethane diisocyanate, 2% tert-butylphenol aldehyde Resin, 3% terpene resin, 2% alumina micropowder, 3% white carbon black nano-capsule powder that step 1 makes, 3% castor oil, 19% dioctyl phthalate and 3% Stir the modified molecular sieve prepared in step 2 for 1 hour to obtain a mixed solution, and discharge the formed mixed solution under the protection of a nitrogen atmosphere to obtain polyurethane glue.

Example 2:

A preparation method of polyurethane glue for environment-friendly sports venues, comprising the following steps: Step 1, according to the weight ratio of 1:3:3, take nano-microcapsule powder, nano-silica and absolute ethanol, mix them in 50KHz Ultrasonic dispersion at high frequency for 20 minutes, then suction filtration under vacuum condition of 0.098MPa, stop suction filtration when there are no more ethanol droplets dripping, take out the filtrate, put it in an oven, and carry out 30℃× After drying for 6 hours and preheating at 50°C×20min, take out the preheated material, put it in a press and pre-press it at 2MPa for 5min, and then heat press it at 5MPa and 150°C for 28min, naturally After being cooled to room temperature, white carbon black nanocapsule powder was prepared, which was set aside;

Step 2. Weigh sodium borate and molecular sieve according to the weight ratio of 2:100, dissolve all the sodium borate in deionized water, then add the weighed molecular sieve, and immerse in a water bath at 50°C for 6 hours to obtain a modified molecular sieve;

Step 3: According to the weight percentage, add polyether polyol into the reaction kettle, and stir at 70°C for 1 hour, then perform vacuum degassing and dehydration treatment for 2.5 hours, cool it to 60°C, and set aside;

Step 4. On the basis of step 3, add the diphenylmethane diisocyanate in the weight percentage, react at 70°C for 2.5h, and cool to 50°C for later use;

Step 5, according to weight percentage, weigh 36% polyoxypropylene glycerol ether, 9% polyoxypropylene propylene glycol ether, 5% 4,4-diphenylmethane diisocyanate, 5% 2,4- Diphenylmethane diisocyanate, 3% tert-butylphenolic resin, 5% terpene resin, 3.5% alumina micropowder, 6.5% white carbon black nano-microcapsule powder that step 1 makes, 10% castor oil , 10% dioctyl phthalate and 7% modified molecular sieve prepared in step 2, stirred for 0.8h to obtain a mixed solution, and discharged the formed mixed solution under the protection of a nitrogen atmosphere to obtain polyurethane glue.

Example 3:

A preparation method of polyurethane glue for environment-friendly sports venues, comprising the following steps: Step 1, according to the weight ratio of 1:3:3, take nano-microcapsule powder, nano-white carbon black and absolute ethanol, mix them in 40KHz Ultrasonic dispersion at high frequency for 25 minutes, and then carry out suction filtration under a vacuum condition of 0.098MPa, stop the suction filtration when there are no more ethanol droplets dripping, take out the filtrate, put it in an oven, and carry out 30°C× After drying for 6 hours and preheating at 50°C×20min, take out the preheated material, put it in a press, pre-press it at 2MPa for 5min, and then press at 5MPa and 155°C for 28min, naturally After being cooled to room temperature, white carbon black nanocapsule powder was prepared, which was set aside;

Step 2. Weigh sodium borate and molecular sieve according to the weight ratio of 2:100, dissolve all the sodium borate in deionized water, then add the weighed molecular sieve, and immerse in a water bath at 50°C for 6 hours to obtain a modified molecular sieve;

Step 3: According to the weight percentage, add polyether polyol into the reaction kettle, and stir at 85°C for 0.5h, then carry out vacuum degassing and dehydration treatment for 2.5h, cool it to 40°C, and set aside ;

Step 4. On the basis of step 3, add the diphenylmethane diisocyanate in the weight percentage, react at 90°C for 2.5h, and cool to 60°C for later use;

Step five, according to weight percentage, weigh 25% polyoxypropylene glycerol ether, 5% polyoxypropylene propylene glycol ether, 10% 4,4-diphenylmethane diisocyanate, 5% 2,4- Diphenylmethane diisocyanate, 3.5% tert-butylphenolic resin, 6.5% terpene resin, 2% aluminum oxide micropowder, 6% white carbon black nano-microcapsule powder that step 1 makes, 7% castor oil , 25% of dioctyl phthalate and 5% of the modified molecular sieve prepared in step 2 were stirred for 1 hour to obtain a mixed solution, and the resulting mixed solution was discharged under the protection of a nitrogen atmosphere to obtain a polyurethane glue.

By above-mentioned embodiment, the glue sample prepared in example 1～3 is tested, and test performance is shown in the table below:

Claims (5)

1. a kind of environmentally friendly sports field polyurethane glue, it is characterised in that：By PPG, diphenylmethane diisocyanate Ester, thermoplastic resin, modified molecular screen, auxiliary agent, castor oil and inorganic filler composition, the percentage by weight of each component are followed successively by： PPG 30 ~ 60%, methyl diphenylene diisocyanate 5 ~ 15%, thermoplastic resin 5 ~ 10%, modified molecular screen 3 ~ 7%, help Agent 10 ~ 25%, castor oil 3 ~ 10% and nanometer inorganic filler 5 ~ 10%, wherein, inorganic filler is 1 by weight ratio：1.5 ~ 2 oxidation Aluminium micro mist and white carbon capsule of nano powder composition, described auxiliary agent is dioctyl phthalate；The alumina powder Granularity is 1 ~ 6 micron, and purity is 98%；White carbon capsule of nano Powder Particle Size is 20 nanometers, purity ＞ 99.5%.

2. a kind of environmentally friendly sports field polyurethane glue according to claim 1, it is characterised in that：Described polyethers is more First alcohol is 2 ~ 5 by weight ratio：1 PPG major ingredient and PPG auxiliary material composition, wherein, PPG major ingredient is Polyoxypropylene glycerol ether, molecular weight is 5000-7000；PPG auxiliary material is polyoxypropylene propyleneglycol ether, molecule Measure as 1000-4000.

3. a kind of environmentally friendly sports field polyurethane glue according to claim 1, it is characterised in that：Described thermoplasticity Resin is 1 by weight ratio：1 ~ 2 tert butyl phenolic resin and terpene resin composition.

4. a kind of environmentally friendly sports field polyurethane glue according to claim 1, it is characterised in that：Described diphenyl Methane diisocyanate is 4,4- methyl diphenylene diisocyanates and/or 2,4- methyl diphenylene diisocyanates.

5. a kind of preparation method of environmentally friendly sports field polyurethane glue according to claim 1, it is characterised in that bag Include following steps：

Step 1: according to 1：3：3 weight ratio, weighs capsule of nano powder, Nano carbon white and absolute ethyl alcohol, 40 after mixing 20 ~ 25min of ultrasonic disperse under ~ 50KHz frequency, then carries out suction filtration in the case where vacuum is 0.098MPa vacuum condition, when There is no suction filtration is stopped during ethanol drips, much filtrate is taken out, is placed in baking oven, 30 DEG C × 6h drying and 50 is carried out successively DEG C × 20min preheating, the material after preheating is taken out, and the precompressed 5min under 2MPa pressure is placed in forcing press, then 28 ~ 30min of hot pressing under the conditions of 5MPa, 145 ~ 155 DEG C, is naturally cooled to after room temperature again, and white carbon Nano capsule powder is made, standby With；

Step 2: according to 2：100 weight ratio, weighs Boratex and molecular sieve, Boratex is all dissolved in deionized water, Then the molecular sieve weighed is added, 6h is impregnated in 50 DEG C of water-bath, obtains modified molecular screen；

Step 3: according to described percentage by weight, PPG is added in reactor, and stirred at 70 ~ 85 DEG C 0.5 ~ 1h, then carries out vacuumizing after degassing dewater treatment 1 ~ 2.5h, is cooled to 40 ~ 60 DEG C, standby；

Step 4: the methyl diphenylene diisocyanate of the percentage by weight is added on the basis of step 3, at 70 ~ 90 DEG C Lower reaction 2.5h, and it is cooled to 40 ~ 60 DEG C, it is standby；

Step 5: according to 1：1.5 ~ 2 weight ratio, weighs the micro- glue of white carbon nanometer made from alumina powder and step one respectively Capsule powder, mixes to obtain inorganic filler；Added on the basis of step 4 the inorganic filler of the percentage by weight, thermoplastic resin, Modified molecular screen prepared by auxiliary agent, castor oil and step 2,0.5 ~ 1h of stirring obtains mixed solution, by shape under nitrogen atmosphere protection Into mixed solution discharging, polyurethane glue is made.