阅读说明：本技术 一种非离子型水性聚氨酯啫喱及其制备方法 (Non-ionic aqueous polyurethane gel and preparation method thereof ) 是由 李维虎 李本祥 戴家兵 汪飞 朱保凌 于 2021-06-23 设计创作，主要内容包括：本发明提供一种非离子型水性聚氨酯啫喱及其制备方法,该水性聚氨酯树脂包括以下原料组分及重量质量份的：大分子多元醇50-140质量份的；多异氰酸酯25-70质量份的；小分子醇类扩链剂0-12质量份的；交联扩链剂0-8质量份的；催化剂0.1-0.5质量份的。其中,所述大分子多元醇以聚乙二醇为主体,占多元醇总质量50％以上。该非离子型水性聚氨酯啫喱呈透明液体或凝胶,可根据需要制成头发定型啫喱水或啫喱膏,不含有害成分,不会刺激人体,安全环保无污染,工艺简单,具有保湿、增亮和定型的功效。(The invention provides a non-ionic aqueous polyurethane gel and a preparation method thereof, wherein the aqueous polyurethane resin comprises the following raw material components in parts by weight: 50-140 parts by mass of macromolecular polyol; 25-70 parts by mass of polyisocyanate; 0-12 parts by mass of a micromolecular alcohol chain extender; 0-8 parts of a cross-linking chain extender; 0.1-0.5 parts by mass of a catalyst. Wherein the macromolecular polyol takes polyethylene glycol as a main body and accounts for more than 50 percent of the total mass of the polyol. The nonionic aqueous polyurethane gel is transparent liquid or gel, can be prepared into hair styling gel water or gel cream according to requirements, does not contain harmful components, does not irritate human bodies, is safe, environment-friendly and pollution-free, has a simple process, and has the effects of moisturizing, brightening and styling.)

1. The preparation method of the nonionic aqueous polyurethane gel is characterized by comprising the following steps:

and (3) prepolymer synthesis stage: reacting 50-140 parts by mass of macromolecular polyol with 25-70 parts by mass of polyisocyanate at 85-95 ℃ for 1.5-2.5 h;

emulsification and post-chain extension stages: adding 0-12 parts by mass of micromolecular alcohol chain extender and 0-8 parts by mass of crosslinking chain extender into the reaction, wherein the total amount of the micromolecular alcohol chain extender and the crosslinking chain extender is more than 4 parts by mass, and reacting for 1.5-2.5h at 75-85 ℃; then adding 0.1-0.5 part by mass of catalyst, and reacting for 2.5-3.5h at 65-75 ℃; adding water for emulsification after the reaction is finished, and then continuously stirring for 30-60min to prepare the nonionic aqueous polyurethane gel;

wherein the macromolecular polyol consists of one or two or more macromolecular polyols including polyethylene glycol, wherein the content of the polyethylene glycol is more than 50 wt%.

2. The method for preparing the non-ionic aqueous polyurethane gel according to claim 1, wherein the macromolecular polyol is prepared from polyethylene glycol and the following components: any one or two or more of polyester polyol, polycarbonate polyol, polytetrahydrofuran polyether polyol, polyethylene oxide polyol, polypropylene oxide polyol, polyester polyether polyol, polysiloxane polyol and bio-based polyol.

3. The method for preparing the non-ionic aqueous polyurethane gel according to claim 1, wherein the polyisocyanate is any one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, methylcycloethyl diisocyanate, hexamethylene diisocyanate, dicycloethylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, tetramethyl m-xylylene diisocyanate, norbornane diisocyanate, dimethyl biphenyl diisocyanate, methylcycloethyl diisocyanate and dimethyl diphenylmethane diisocyanate.

4. The method for preparing the non-ionic aqueous polyurethane gel according to claim 1, wherein the polyisocyanate is isophorone diisocyanate.

5. The method for preparing the non-ionic waterborne polyurethane gel according to claim 1, wherein the small molecular alcohol chain extender is any one or a combination of two or more of dimethylolpropionic acid and dimethylolbutyric acid, ethylene glycol, 1, 4-butanediol, 1, 2-propanediol, neopentyl glycol, methylpropanediol, 1, 6-ethanediol, 1, 3-propanediol, butylethylpropanediol, diethylpentanediol, trimethylpentanediol, ethylhexanediol, dodecacarbodiimide and cyclohexanediol.

6. The method for preparing the non-ionic aqueous polyurethane gel according to claim 1, wherein the crosslinking chain extender is any one or a combination of two or more of trimethylolpropane, glycerol, trimethylolethane, 1,2, 6-hexanetriol, pentaerythritol and trishydroxyethyl isocyanurate.

7. The method for preparing the non-ionic aqueous polyurethane gel according to claim 1, wherein the catalyst is an organic bismuth catalyst.

8. A non-ionic aqueous polyurethane gel made by the method of any one of claims 1-7.

Technical Field

The invention relates to the technical field of high molecular polymers, and particularly discloses a nonionic aqueous polyurethane gel and a preparation method thereof.

Background

The water-based polyurethane has the characteristics of safety, environmental protection and the like, and is applied to more and more fields, and the cosmetics are also one application direction. The gel film-forming agent in the market at present mainly comprises acrylic resin, the acrylic resin uses more solvents and diluents in the process of preparing the gel film-forming agent, the solvents and the diluents have large influence on the environment after being volatilized, simultaneously, the waste of resources is caused, and the residual part is harmful to human bodies. Therefore, a method for preparing the jelly film-forming agent which is environment-friendly and harmless to human bodies is urgently needed to be searched.

Disclosure of Invention

The invention aims to overcome the defects of environmental and human body hazards of acrylic resin gel film-forming agents in the prior art, and provides the non-ionic water-based polyurethane gel which is environment-friendly and harmless to human bodies and the preparation method thereof.

In order to solve the technical problem, the technical scheme is that the preparation method of the nonionic aqueous polyurethane gel comprises the following steps:

and (3) prepolymer synthesis stage: reacting 50-140 parts by mass of macromolecular polyol with 25-70 parts by mass of polyisocyanate at 85-95 ℃ for 1.5-2.5 h;

emulsification and post-chain extension stages: adding 0-12 parts by mass of micromolecular alcohol chain extender and 0-8 parts by mass of crosslinking chain extender into the reaction, wherein the total amount of the micromolecular alcohol chain extender and the crosslinking chain extender is more than 4 parts by mass, and reacting for 1.5-2.5h at 75-85 ℃; then adding 0.1-0.5 part by mass of catalyst, and reacting for 2.5-3.5h at 65-75 ℃; adding water for emulsification after the reaction is finished, and then continuously stirring for 30-60min to prepare the nonionic aqueous polyurethane gel;

wherein the macromolecular polyol consists of one or two or more macromolecular polyols including polyethylene glycol, wherein the content of the polyethylene glycol is more than 50 wt%.

The preparation method of the nonionic aqueous polyurethane gel is further improved as follows:

preferably, the macromolecular polyol is composed of any one or two or more of polyethylene glycol and polyester polyol, polycarbonate polyol, polytetrahydrofuran ether polyol, polyethylene oxide polyol, polypropylene oxide polyol, polyester ether polyol, polysiloxane polyol and bio-based polyol.

Preferably, the polyisocyanate is any one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, methylcycloethyl diisocyanate, hexamethylene diisocyanate, dicycloethyl methane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, cyclohexanedimethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcycloethyl diisocyanate, and dimethyldiphenylmethane diisocyanate.

Preferably, the polyisocyanate is isophorone diisocyanate.

Preferably, the small molecular alcohol chain extender is any one or a combination of two or more of dimethylolpropionic acid, dimethylolbutyric acid, ethylene glycol, 1, 4-butanediol, 1, 2-propanediol, neopentyl glycol, methylpropanediol, 1, 6-ethanediol, 1, 3-propanediol, butylethylpropanediol, diethylpentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol and cyclohexanediol.

Preferably, the crosslinking chain extender is any one or a combination of two or more of trimethylolpropane, glycerol, trimethylolethane, 1,2, 6-hexanetriol, pentaerythritol and trishydroxyethyl isocyanurate.

Preferably, the catalyst is an organobismuth catalyst.

In order to solve the technical problem, the invention adopts another technical scheme that the nonionic aqueous polyurethane gel is prepared by any one of the preparation methods.

Compared with the prior art, the invention has the beneficial effects that:

1) the conventional processing technology of the nonionic aqueous polyurethane comprises a prepolymer synthesis step, an emulsification-post chain extension step and a desolventizing step, wherein the prepolymer synthesis process is divided into 1 step to 3 steps according to needs, and the main raw materials comprise macromolecular polyol, polyisocyanate, a micromolecular chain extender, a hydrophilic chain extender (anions and cations can be used), a catalyst, acetone or other solvents (mainly playing roles in reducing viscosity and dissolving a micromolecular alcohol chain extender); in the emulsification-post chain extension stage, acetone is generally used for reducing viscosity, then a dispersion machine is used for adding water for emulsification, and then a post chain extender is added; and in the desolventizing stage, other solvents such as acetone and the like are removed.

However, the conventional processing technology of the nonionic aqueous polyurethane is not suitable for the nonionic aqueous polyurethane, because the viscosity of the aqueous polyurethane used for the gel is high, if solvents such as acetone for reducing the viscosity are added, the solvents cannot be completely removed, the residual solvents have high taste, and the solvents are harmful to human bodies; if solvents such as acetone for reducing viscosity are not added, the solvents cannot be uniformly dispersed during chain extension, local sudden aggregation can be caused, the state of the resin is not uniform, and the use is influenced.

The preparation process of the nonionic waterborne polyurethane gel comprises a prepolymer synthesis stage and an emulsification and post-chain extension stage, wherein the main raw materials of the prepolymer synthesis stage are macromolecular polyol, polyisocyanate, a micromolecular alcohol chain extender and a micromolecular cross-linking agent, wherein the macromolecular polyol is a soft segment, other raw materials are hard segments, waterborne polyurethanes with different hardness can be obtained by controlling the proportion, and no solvent is used in the stage; in the emulsification stage, a solvent is not used for reducing viscosity, the viscosity is controlled by controlling-nco content (namely the content of polyisocyanate radical minus the content of hydroxyl), so that the emulsification difficulty caused by overlarge viscosity is prevented, and meanwhile, water is directly added into a dispersion machine for emulsification in a high-temperature state; because the polyethylene glycol accounts for more than 50 wt% of the macromolecular polyol, the hydrophilicity of the waterborne polyurethane is mainly provided by the polyethylene glycol, and the addition of a neutralizer is avoided; and in the post chain extension stage, no micromolecule amine chain extender is added, and the residual-nco slowly reacts with water in a continuous stirring mode to prevent gelation. The finished product of waterborne polyurethane is directly obtained after the reaction is carried out for 30-60min, and simultaneously, the desolventizing process is avoided.

2) The nonionic aqueous polyurethane gel prepared by the invention is transparent liquid or gel, the main solvent is water, no harm is caused to the environment and human body in the drying process, and the gel can play a role in moisturizing, brightening and shaping when used in the formula of the gel. The preparation process does not add micromolecule amine chain extender and solvent, does not contain harmful components, does not stimulate human bodies, is safe, environment-friendly and pollution-free, has simple synthesis process, can change the hardness of the dried resin by adjusting the proportion of polyisocyanate, cross-linking chain extender and macromolecular polyol in the formula to prepare the setting gel with different hardness, has the effects of moisturizing, brightening and setting, and can be widely applied to the setting and moisturizing gel.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.

Comparative example 1

Dehydrating 30g of polyethylene glycol polyol (molecular weight of 2000) and 80g of polytetrahydrofuran ether polyol (molecular weight of 2000) at 105 ℃ for 1h, then cooling to 50 ℃, adding 50g of isophorone diisocyanate, heating to 90 ℃, keeping the temperature and reacting for 2 hours, measuring the NCO content within two hours, cooling to 85 ℃ when the theoretical value is reached, then adding 4.5g of methyl propylene glycol and 3g of dimethylolpropionic acid to react for 2 hours at 85 ℃, then adding 0.32g of organic bismuth Coscat83, adding 25g of acetone to reduce viscosity, reacting for 3 hours at 70 ℃, measuring the NCO content after the reaction is finished, then adding 80g of acetone to reduce viscosity, then adding 2.15g of triethylamine to neutralize, adding 275g of deionized water under high-speed shearing, after the emulsion is opened, slowly dripping 3.6g of ethylenediamine under high-speed stirring, continuing to stir for 2-5 minutes, removing acetone after the reaction is finished, thus obtaining the waterborne polyurethane resin sample 6 with the solid content of 39%.

The gloss of sample 3 of the aqueous polyurethane resin was determined to be 74% by testing (test standard GB1743-1979(1989) gloss determination of paint film). Spreading and solidifying the emulsion of the sample 6 to obtain a water-based polyurethane film, and testing the tensile strength and the elongation at break of the obtained water-based polyurethane film according to GB/T1040-92 plastic tensile property experiment method, wherein the test result is as follows: the modulus was 2.545MPa, the tensile strength was 17.6MPa, and the elongation at break was 566.3%.

Example 1

50g of polyethylene glycol polyol (molecular weight is 2000) is dehydrated for 1 hour at 105 ℃, then the temperature is reduced to 50 ℃, 25g of isophorone diisocyanate is added, the temperature is increased to 90 ℃, the heat preservation reaction is carried out for 2 hours, the NCO content is measured for two hours, the temperature is reduced to 80 ℃ when the theoretical value is reached, then 4.5g of 1, 4-butanediol is added for reaction for 2 hours at 80 ℃, then 0.16g of organic bismuth Coscat83 is added, the reaction is carried out for 3 hours at 70 ℃, the NCO content is measured after the reaction is finished, then 147g of deionized water is added under high-speed shearing, and the mixture is stirred for 30 minutes, so that the waterborne polyurethane resin sample 1 with the solid content of 36 percent is obtained.

The gloss of the aqueous polyurethane resin sample 1 was 77% (test standard GB1743-1979(1989) gloss determination of paint film), which indicates that the resin of the present invention has good gloss. Spreading and solidifying the emulsion of the sample 1 to obtain a water-based polyurethane film, and testing the tensile strength and the elongation at break of the obtained water-based polyurethane film according to GB/T1040-92 plastic tensile property experimental method to obtain a test result; the modulus was 3.773MPa, the tensile strength was 12.5MPa, and the elongation at break was 330.2%. Therefore, when the aqueous polyurethane resin is applied to the formula of the gel, the fixed gel with good glossiness can be obtained.

Example 2

50g of polyethylene glycol polyol (molecular weight is 1000) is dehydrated for 1 hour at 105 ℃, then the temperature is reduced to 50 ℃, 50g of isophorone diisocyanate is added, the temperature is increased to 90 ℃, the heat preservation reaction is carried out for 2 hours, the NCO content is measured for two hours, the temperature is reduced to 80 ℃ when the theoretical value is reached, 4.5g of 1, 4-butanediol is added for reaction for 2 hours at 80 ℃, then 0.22g of organic bismuth Coscat83 is added, the reaction is carried out for 3 hours at 70 ℃, the NCO content is measured after the reaction is finished, 194g of deionized water is added under high-speed shearing, and the mixture is stirred for 30 minutes, so that the waterborne polyurethane resin sample 2 with the solid content of 35 percent is obtained.

The glossiness of the waterborne polyurethane resin sample 2 is 80 percent (the detection standard is GB1743-1979(1989) which is a paint film glossiness measuring method), which shows that the resin has good glossiness. Spreading and solidifying the emulsion of the sample 2 to obtain a water-based polyurethane film, and testing the tensile strength and the elongation at break of the obtained water-based polyurethane film according to GB/T1040-92 plastic tensile property experiment method, wherein the test result is as follows: the modulus was 5.428MPa, the tensile strength was 18.2MPa, and the elongation at break was 213.2%. Therefore, when the aqueous polyurethane resin is applied to the formula of the gel, the fixed gel with good glossiness can be obtained.

Example 3

50g of polyethylene glycol polyol (molecular weight 2000) and 50g of polytetrahydrofuran ether polyol (molecular weight 2000) are dehydrated for 1 hour at 105 ℃, then the temperature is reduced to 50 ℃, 50g of isophorone diisocyanate is added, the temperature is increased to 90 ℃, the temperature is kept for reaction for 2 hours, the NCO content is measured for two hours, the temperature is reduced to 80 ℃ when the NCO content reaches the theoretical value, 4.5g of methyl propylene glycol is added for reaction for 2 hours at 80 ℃, then 0.32g of organic bismuth Coscat83 is added, the reaction is carried out for 3 hours at 70 ℃, the NCO content is measured after the reaction is finished, 253g of deionized water is added under high-speed shearing, and the mixture is stirred for 30 minutes, so that the waterborne polyurethane resin sample 3 with the solid content of 38 percent is obtained.

The glossiness of the waterborne polyurethane resin sample 3 is 75 percent (the detection standard is GB1743-1979(1989) which is a paint film glossiness measuring method), which shows that the resin has good glossiness. Spreading and solidifying the emulsion of the sample 3 to obtain a water-based polyurethane film, and testing the tensile strength and the elongation at break of the obtained water-based polyurethane film according to GB/T1040-92 plastic tensile property experiment method, wherein the test result is as follows: the modulus was 1.997MPa, the tensile strength was 11.9MPa, and the elongation at break was 456.3%. Therefore, when the aqueous polyurethane resin is applied to the formula of the gel, the fixed gel with good glossiness can be obtained.

Example 4

50g of polyethylene glycol polyol (molecular weight is 2000) and 20g of polycaprolactone polyol (molecular weight is 1000) are dehydrated for 1 hour at 105 ℃, then the temperature is reduced to 50 ℃, 30g of isophorone diisocyanate and 10g of hexamethylene diisocyanate are added, the temperature is increased to 90 ℃, the heat preservation reaction is carried out for 2 hours, the NCO content is measured for two hours, when the theoretical value is reached, the temperature is reduced to 80 ℃, 6.21g of methyl propylene glycol and 1.8g of trihydroxypropane are added for reaction for 2 hours at 80 ℃, then 0.3g of organic bismuth Coscat83 is added, the reaction is carried out for 3 hours at 70 ℃, the NCO content is measured after the reaction is finished, 186g of deionized water is added under high-speed shearing, and after 30 minutes of stirring, the waterborne polyurethane resin sample 4 is obtained, wherein the solid content is 40%.

The glossiness of the waterborne polyurethane resin sample 4 is 81 percent (the detection standard is GB1743-1979(1989) which is a paint film glossiness measuring method), which shows that the resin has good glossiness. Spreading and solidifying the emulsion of the sample 4 to obtain a water-based polyurethane film, and testing the tensile strength and the elongation at break of the obtained water-based polyurethane film according to GB/T1040-92 plastic tensile property experiment method, wherein the test result is as follows: the modulus was 3.576MPa, the tensile strength was 16.8MPa, and the elongation at break was 326.1%. Therefore, when the aqueous polyurethane resin is applied to the formula of the gel, the fixed gel with good glossiness can be obtained.

Example 5

60g of polyethylene glycol polyol (molecular weight is 1000) and 20g of polypropylene oxide polyol (molecular weight is 1000) are dehydrated for 1h at 105 ℃, then the temperature is reduced to 50 ℃, 40g of isophorone diisocyanate and 30g of dicyclohexylmethane diisocyanate are added, the temperature is increased to 90 ℃, the reaction is kept for 2h, the NCO content is measured for two hours, the temperature is reduced to 80 ℃ when the NCO content reaches the theoretical value, then 8.2g of 1, 4-butanediol and 2.8g of trihydroxypropane are added for reaction for 2h at 80 ℃, then 0.34g of organic bismuth Coscat83 is added, the reaction is carried out for 3h at 70 ℃, the NCO content is measured after the reaction is finished, 237g of deionized water is added under high-speed shearing, and the mixture is stirred for 30min, so that the waterborne polyurethane resin sample 5 with the solid content of 37% is obtained.

The glossiness of the waterborne polyurethane resin sample 5 is 83 percent (the detection standard is GB1743-1979(1989) which is a paint film glossiness measuring method), which shows that the resin has good glossiness. Spreading and solidifying the emulsion of the sample 4 to obtain a water-based polyurethane film, and testing the tensile strength and the elongation at break of the obtained water-based polyurethane film according to GB/T1040-92 plastic tensile property experiment method, wherein the test result is as follows: the modulus was 4.428MPa, the tensile strength was 14.9MPa, and the elongation at break was 244.6%. Therefore, when the aqueous polyurethane resin is applied to the formula of the gel, the fixed gel with good glossiness can be obtained.

Example 6

80g of polyethylene glycol polyol (molecular weight of 2000) and 40g of polytetrahydrofuran ether polyol (molecular weight of 2000) are dehydrated for 1h at 105 ℃, then the temperature is reduced to 50 ℃, 32g of isophorone diisocyanate is added, the temperature is increased to 90 ℃, the temperature is kept for reaction for 2h, the NCO content is measured for two h, when the NCO content reaches the theoretical value, the temperature is reduced to 80 ℃, 3.2g of trihydroxy propane is added for reaction for 2h at 80 ℃, 0.4g of organic bismuth Coscat83 is added, the reaction is carried out for 3h at 70 ℃, the NCO content is measured after the reaction is finished, 233g of deionized water is added under high-speed shearing, and after stirring for 30min, the waterborne polyurethane resin sample 6 with the solid content of 40% is obtained.

The gloss of the aqueous polyurethane resin sample 6 was determined to be 75% by test (test standard GB1743-1979(1989) gloss determination of paint film), which indicates that the resin of the present invention has good gloss. Spreading and solidifying the emulsion of the sample 6 to obtain a water-based polyurethane film, and testing the tensile strength and the elongation at break of the obtained water-based polyurethane film according to GB/T1040-92 plastic tensile property experiment method, wherein the test result is as follows: the modulus was 2.270MPa, the tensile strength was 8.9MPa, and the elongation at break was 536.3%. Therefore, when the aqueous polyurethane resin is applied to the formula of the gel, the fixed gel with good glossiness can be obtained.

From the test data of comparative example 1 and examples 1-6, it can be seen that: the preparation method has the advantages that a neutralizer is not required to be added in the preparation process of the nonionic waterborne polyurethane gel, no solvent is added in the emulsification and post-chain extension stages for viscosity reduction, water is directly added in a dispersion machine for emulsification at a high temperature, no post-chain extender is added, the main solvent is water, and the method is harmless to human bodies; the prepared nonionic aqueous polyurethane gel has good glossiness and strength meeting the use requirement; the hardness of the dried resin can be changed by adjusting the proportion of soft and hard segments in the formula so as to prepare the setting gel with different hardness (modulus).

It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.