CN113861377B

CN113861377B - Aqueous polyurethane-polyurea dispersion resin and preparation method and application thereof

Info

Publication number: CN113861377B
Application number: CN202010613300.2A
Authority: CN
Inventors: 胡海东; 周操; 晋云全; 纪学顺; 郝宝祥; 孙家宽
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2020-06-30
Filing date: 2020-06-30
Publication date: 2023-07-14
Anticipated expiration: 2040-06-30
Also published as: CN113861377A

Abstract

The invention belongs to the technical field of glass fiber infiltration film forming agents, and particularly relates to a waterborne polyurethane-polyurea dispersion resin, a preparation method and application thereof, wherein the resin is prepared from the following raw materials by reaction: s1) diisocyanate; s2) a polymer polyol; s3) nonionic hydrophilic compound; s4) a polyol small-molecule chain extender containing active hydrogen, wherein the molecular weight is 30-200g/mol; s5) an active hydrogen-containing sulfonic acid-type hydrophilic chain extender; s6) an amine small molecule chain extender containing active hydrogen, wherein the molecular weight is 30-200g/mol; s7) monoamine small molecule end capping agent containing active hydrogen, and the molecular weight is 30-300g/mol. The aqueous polyurethane-polyurea dispersion resin can maintain good compounding stability with cationic components in the impregnating compound, has excellent mechanical properties, high-temperature yellowing resistance and solvent resistance, and has good thermal weightlessness.

Description

Aqueous polyurethane-polyurea dispersion resin and preparation method and application thereof

Technical Field

The invention belongs to the technical field of glass fiber infiltration film forming agents, and particularly relates to a waterborne polyurethane-polyurea dispersion resin and a preparation method and application thereof.

Background

The polyurethane resin has excellent performance and wide application, and is applied to various fields of transportation, clothing, construction, spinning, synthetic leather and the like. The waterborne polyurethane is used as one branch of polyurethane resin, and has excellent performance, high strength after film formation, good toughness and good elasticity; when the glass fiber sizing agent is applied to the field of glass fiber sizing treatment, the bonding performance and the film forming property are excellent, the glass fiber can be effectively protected, meanwhile, the polarity is strong, the glass fiber sizing agent is well combined with most matrix resin, and the problem of non-ideal interface combination can be well solved, so the glass fiber sizing agent can be used as a main film former component of the enhanced glass fiber yarn sizing agent. However, when the glass fiber impregnating compound is compounded, a large amount of anionic auxiliary agents and cationic auxiliary agents are added into the formula system, so that challenges are presented to the compounding stability of the resin. Traditional ionic aqueous polyurethane can not meet the industry requirement, and glass fiber infiltration film forming agents containing the aqueous polyurethane used in China are imported and are high in price. Thus, some studies and researches on aqueous polyurethane film forming agents for glass fibers have been conducted.

For example, patent document CN103224602a discloses a waterborne polyurethane film-forming agent for glass fibers and a preparation method thereof, wherein macromolecular polyol and aliphatic diisocyanate are used as raw materials to react, a carboxylic acid type hydrophilic chain extender is used as a hydrophilic monomer, and the hydrophilic chain extender is neutralized and dispersed in water to prepare the waterborne polyurethane film-forming agent; and organic solvent and neutralizer are introduced in the synthesis process, so that the VOC content is high, the current environmental protection trend is not facilitated, and the industrial requirements are hardly met.

For example, patent document CN104387554B discloses a preparation method of a polyurethane modified epoxy resin for a glass fiber film forming agent, which is applied to the glass fiber film forming agent by adding an active functional group to perform ring opening reaction with an epoxy group so that the glass fiber has good stiffness and bundling property; however, the added epoxy resin has poor self stability, is very unstable in a polyurethane modified resin system and is easy to generate sedimentation and delamination; and because of the characteristics of the epoxy resin, the film forming property after curing is poor, and a large amount of organic solvent is introduced in the synthesis process to dilute the epoxy, the epoxy resin is contrary to the development trend of the current industry, and the comprehensive cost performance is not high.

Therefore, the waterborne polyurethane resin with excellent comprehensive performance and simultaneously with the environment-friendly idea is more and more favored by people. However, in the use process of the traditional aqueous polyurethane resin as a film forming agent, the effective components of the aqueous polyurethane resin in the impregnating solution have low proportion, and the quantity of functional groups which can react with the curing agent is limited when the curing agent is added for crosslinking; in addition, the compounding stability of the aqueous polyurethane resin and other cationic assistants in the impregnating solution is also a technical problem to be solved. Therefore, the traditional aqueous polyurethane resin has poor comprehensive performance and low strength when being used as a film forming agent, and can not meet the processing and use requirements of glass fibers. In conclusion, an aqueous polyurethane resin with excellent performance and excellent ion stability in compounding is developed, and becomes an important point in the current research of the field of aqueous glass fibers.

Disclosure of Invention

Aiming at the problems of the existing film forming agent for glass fibers, the invention provides the aqueous polyurethane-polyurea dispersion resin, the preparation method and the application thereof, wherein the aqueous polyurethane-polyurea dispersion resin has higher formula stability, can keep good compound stability with other cationic components in a sizing agent when being used for the glass fiber film forming agent, ensures high stability of a paint formulation emulsion, can obtain higher strength and mechanical property, has excellent high-temperature yellowing resistance and solvent resistance, and has better thermal weight loss, and can meet the high-temperature process requirements in the glass fiber processing process.

In order to achieve the above purpose, the technical scheme provided by the invention is as follows:

in one aspect, an aqueous polyurethane-polyurea dispersion resin is provided, prepared by reacting raw materials comprising the following components:

s1) at least one diisocyanate;

s2) at least one polymer polyol having an average molecular weight of 500 to 3000g/mol, preferably 1000 to 2000g/mol; the polymer polyol is preferably a polyether glycol and/or a polyester glycol;

wherein the molar ratio of component S1) to component S2) is from 2:1 to 5:1 (e.g., 2.4:1, 2.8:1, 3.0:1, 3.8:1, 4.5:1, 4.7:1), preferably from 2.5:1 to 4:1;

S3) at least one nonionic hydrophilic compound having an average molecular weight of 300 to 2000g/mol, preferably 500 to 1500g/mol; the nonionic hydrophilic compound is preferably monohydric alcohol and/or dihydric alcohol with main chain and/or side chain containing polyethylene oxide chain segments;

s4) at least one polyol small molecule chain extender containing active hydrogen, wherein the molecular weight of the polyol small molecule chain extender is 30-200g/mol;

s5) at least one sulfonic acid type hydrophilic chain extender containing active hydrogen;

s6) at least one amine small molecule chain extender containing active hydrogen, preferably diamine small molecule chain extender containing active hydrogen and/or hydrazine small molecule chain extender containing active hydrogen; the molecular weight of the amine small molecular chain extender containing active hydrogen is 30-200g/mol;

s7) at least one monoamine small molecule end-capping agent containing active hydrogen, wherein the molecular weight of the monoamine small molecule end-capping agent is 30-300g/mol.

According to the aqueous polyurethane-polyurea dispersion resin provided by the invention, in some embodiments, the main structural general formula of the aqueous polyurethane-polyurea dispersion resin can be shown as formula I:

in the method, in the process of the invention,

R ₁ can be selected from

R ₂ Can be selected from

R ₃ Can be selected from

Wherein m has a value of 3 to 8 (for example, n=4, 5, 6, 7);

n has a value of 10 to 20 (for example, n=12, 14, 16, 18).

According to the aqueous polyurethane-polyurea dispersion resins provided herein, in some examples, the following components are used in amounts based on the sum of the weights of the components (e.g., 100 wt.%):

s1) is used in an amount of 10 to 45wt% (e.g., 12wt%, 18wt%, 20wt%, 28wt%, 30wt%, 40 wt%), preferably 15 to 25wt%;

s2) is used in an amount of 45-75wt% (e.g., 48wt%, 50wt%, 60wt%, 65wt%, 72 wt%), preferably 55-70wt%;

s3) is used in an amount of 3 to 10wt% (e.g., 4wt%, 6wt%, 7wt%, 9 wt%), preferably 5 to 8wt%;

s4) is used in an amount of 0-10wt% (e.g., 0.1wt%, 1wt%, 1.5wt%, 3wt%, 4wt%, 6wt%, 7wt%, 9 wt%), preferably 2-8wt%;

s5) is used in an amount of 0.1 to 1wt% (e.g., 0.15wt%, 0.3wt%, 0.4wt%, 0.6wt%, 0.9 wt%), preferably 0.2 to 0.8wt%;

s6) is used in an amount of 0.5-5wt% (e.g., 0.6wt%, 2wt%, 3wt%, 3.5wt%, 4.5 wt%), preferably 1-4wt%;

s7) is used in an amount of 1 to 5wt% (e.g., 1.5wt%, 2.5wt%, 3.5wt%, 4.5 wt%), preferably 2 to 3wt%.

In some examples, component S1) is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate, preferably from one or more of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), and dicyclohexylmethane diisocyanate.

In some examples, component S2) is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, 1, 4-butanediol polyadipate diol, neopentyl glycol polyadipate diol, 1, 6-hexanediol polyadipate diol, and neopentyl glycol-1, 6-hexanediol polyadipate diol, preferably neopentyl glycol-1, 6-hexanediol polyadipate diol (e.g., CMA 654).

In some examples, the polymerized units (of the polyethylene oxide segment) of component S3) contain ethylene oxide in a proportion of 90 to 100wt% based on the total weight of the nonionic hydrophilic compound; preferably, the nonionic hydrophilic compound is selected from polyethylene oxide ether glycols and/or polyethylene glycol methyl ethers, more preferably from polyethylene oxide ether glycols (or difunctional polyethoxy ethers). For example, the component S3) may be Tego Chemie Co

Ymer of D-3403, perstop company ^TM One or more of N120 and MPEG1200 of Korean music, inc., preferably Ymer of Perstop, inc ^TM N120 and/or MPEG1200 of korea music day company.

In some examples, component S4) is selected from one or more of 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol, preferably from one or more of 1, 4-butanediol, 1, 6-hexanediol and neopentyl glycol. In some embodiments, the amount of component S4) added is primarily adjusted based on the molar ratio of component S1) to component S2) (i.e., the R value.

In some examples, component S5) is selected from one or more of sodium ethylenediamine-ethanesulfonate, sodium 2- (2-aminoethyl) aminopropanesulfonate, sodium 1, 4-butanediol-2-sulfonate, and sodium 1, 2-dihydroxy-3-propanesulfonate, preferably sodium ethylenediamine-ethanesulfonate.

In some examples, component S6) is selected from one or more of ethylenediamine, hydroxyethylethylenediamine, hexamethylenediamine, pentamethylenediamine, diethylenetriamine, isophoronediamine and 4, 4-diphenylmethane diamine, preferably from hydroxyethylethylenediamine and/or isophoronediamine.

In some examples, component S7) is selected from one or more of cyclohexylamine, diethylamine, tris-hydroxymethyl-aminomethane, ethanolamine, diethanolamine, and 2-amino-2-methyl-1-propanol; in a preferred embodiment, component S7) is tris (hydroxymethyl) aminomethane.

In some examples, the feedstock further comprises, based on the total weight of components S1) -S7):

water in an amount of 100 to 250 wt.%, preferably 150 to 200 wt.%, based on the total weight of components S1) to S7);

a low boiling point organic solvent added in an amount of 1.2 to 2 times the total weight of the components S1) to S7); in some examples, the low boiling point organic solvent is selected from acetone and/or butanone, preferably acetone;

a catalyst added in an amount of 0.01 to 0.05wt% (e.g., 0.015wt%, 0.025wt%, 0.035wt%, 0.045 wt%), preferably 0.02 to 0.03 wt%) based on the total weight of component S1) -component S7); in some examples, the catalyst is selected from dibutyltin dilaurate, cobalt octoate, or BiCat8108, preferably BiCat8108.

In another aspect, there is also provided a method for preparing the aqueous polyurethane-polyurea dispersion resin as described above, comprising the steps of:

(1) Uniformly mixing the component S1), the component S2), the component S3), the component S4), the catalyst and the low-boiling point organic solvent to react until NCO in the system basically reaches or approaches to a theoretical value, and generating isocyanate-terminated prepolymer;

(2) Adding the low-boiling point organic solvent into the reaction system in the step (1), and dissolving and diluting materials in the system to obtain diluted isocyanate-terminated prepolymer;

(3) Adding an aqueous solution containing the component S5) and the component S6) into the reaction system of the step (2) to perform chain extension reaction, and then adding water to perform shearing dispersion;

(4) And (3) adding an aqueous solution containing the component S7) into the reaction system of the step (3) to carry out end-capping reaction to obtain a coarse emulsion containing polyurethane-polyurea.

Optionally, the low-boiling point organic solvent is partially or completely removed by reduced pressure distillation to obtain the aqueous polyurethane-polyurea dispersion resin. The treatment apparatus and treatment process for reduced pressure distillation described herein are well known to those skilled in the art.

According to the preparation method provided by the invention, in some examples, the solid content of the aqueous polyurethane-polyurea dispersion resin is 40-60%, preferably 45-55%.

In some examples, the average particle size of the aqueous polyurethane-polyurea dispersion resin is 200 to 600nm, preferably 300 to 500nm.

In some examples, the temperature of the reaction of step (1) is 70-80 ℃ (e.g., 72 ℃, 75 ℃, 78 ℃).

In some examples, the process conditions of the dissolution dilution of step (2) include: the dissolution temperature is 40-50deg.C (e.g., 45deg.C), and the dissolution time is 5-10min (e.g., 6min, 8 min).

In some examples, the aqueous solution containing component S5) and component S6) of step (3) is used in an amount of 4 to 6 times (e.g., 5 times) the sum of the masses of both component S5) and component S6). The aqueous solution containing the component S5) and the component S6) described herein may refer to an aqueous solution formulated with the component S5) and the component S6) as solutes and water as a solvent. In some examples, the process conditions of the chain extension reaction include: the reaction temperature is 40-50deg.C (e.g., 45deg.C), and the reaction time is 15-25min (e.g., 20 min).

In some examples, the amount of water in the aqueous solution containing component S7) of step (4) is 4-6 times (e.g., 5 times) the mass of component S7). The aqueous solution containing the component S7) described herein may refer to an aqueous solution formulated with the component S7) as a solute and water as a solvent. In some examples, the capping reaction has a reaction time of 8-10 minutes (e.g., 9 minutes).

The invention also provides application of the aqueous polyurethane-polyurea dispersion resin in preparing the glass fiber infiltration film forming agent, wherein the aqueous polyurethane-polyurea dispersion resin is prepared by the preparation method or the preparation method.

According to the application provided by the invention, preferably, in the process of preparing the glass fiber infiltration film-forming agent, the aqueous polyurethane-polyurea dispersion resin is compounded with the cationic auxiliary agent. The amount of the cationic auxiliary agent can be determined according to the use requirement of the glass fiber infiltration film-forming agent.

In some examples, the cationic adjuvant is selected from one or more of dimethylallyl ammonium chloride, calcium sulfate, and cetyltrimethylammonium bromide; in a preferred embodiment, the cationic adjuvant is cetyltrimethylammonium bromide.

According to the invention, the nonionic hydrophilic compound component is introduced and used as a hydrophilic main body in the waterborne polyurethane-polyurea resin, and the dosage of the added ionic hydrophilic compound (such as a sulfonic acid type hydrophilic chain extender) is adjusted, so that a compound system formed by the resin and a cationic auxiliary agent can be stabilized when the dispersion resin is applied to the glass fiber infiltration film forming agent, and the excellent stability of the compound system is ensured.

The chain extension can be carried out under the condition of high ureido content and the chain extension proportion can be adjusted by designing the addition proportion of each component in the preparation process of the resin, so that a polyurethane resin chain segment with large molecular weight can be obtained, and the high-temperature yellowing resistance, solvent resistance and mechanical property of the obtained resin can be improved; compared with the traditional low-molecular-weight two-component aqueous polyurethane resin, by introducing high-functionality end capping groups into the system, the high hydroxyl content can be realized under the condition of ensuring that the resin has a large molecular weight, and the problems of low initial molecular weight, poor performance after subsequent curing and the like of the resin are solved.

The system for preparing the aqueous polyurethane-polyurea dispersoid is an NCO excess system, the dosage of the component S7) needs to be controlled, the excessive dosage can lead to a higher end-capping rate, the molecular weight of the obtained polyurethane chain segment is smaller, and the excessive NCO is blocked and cannot be further chain-extended with water to increase the molecular weight, so that the performance of a product can be influenced.

Therefore, the aqueous polyurethane-polyurea resin obtained by the invention has excellent ion stability, and can meet the compounding requirement of being used as a glass fiber infiltration film forming agent; meanwhile, the aqueous polyurethane-polyurea resin has higher strength and mechanical property, excellent high-temperature yellowing resistance and solvent resistance, and good thermal weightlessness, and can meet the high-temperature process requirements in the glass fiber processing process.

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

(1) The micro-phase separation degree of the aqueous polyurethane-polyurea dispersion resin can reach an optimal state by the special proportion of soft and hard segments (the proportion of the components S1/S2, namely R value) through the formula design, and the prepared aqueous polyurethane-polyurea dispersion resin has excellent film forming property and solvent resistance, can shift the thermal weight loss rate of the aqueous polyurethane-polyurea dispersion resin to be higher than Wen Fangxiang, and can meet the thermal weight loss requirement of the glass fiber processing process at 300-400 ℃;

(2) The hydrophilic compound component (component S3) containing nonionic groups is introduced in the synthesis process of the aqueous polyurethane-polyurea dispersion resin and is used as a hydrophilic main body, and the hydrophilic compound component and the hydrophilic main body are reasonably matched under the condition of adding a small amount of sulfonic acid type hydrophilic monomer (component S5), so that the ion stability of the obtained resin can be enhanced, and the stability of the paint emulsion in the process of being used for a glass fiber film forming agent is ensured to be improved;

the water-based polyurethane dispersion resin and the cationic auxiliary agent are ensured to have good complexing property, and other solvents are not introduced in the synthesis process, so that the water-based polyurethane dispersion resin meets the current environmental protection trend;

(3) In the preparation process of the aqueous polyurethane-polyurea dispersion resin, the chain extension can be ensured under the condition of higher ureido content by adjusting the addition amount of the component S6), so that the high-temperature yellowing resistance and the mechanical property of the obtained dispersion resin are improved; in the preparation process, by introducing a very small amount of amino end-capping ratio (namely adding a small amount of component S7), the isocyanate end-capped aqueous polyurethane prepolymer can be further subjected to chain extension reaction with water under the condition of ensuring high content of active functional groups, so that the high molecular weight, gao Niaoji and high content of active functional groups of the aqueous polyurethane-polyurea dispersion resin are realized, and the obtained resin can be fully cured and crosslinked by the curing agent under the premise of ensuring the excellent performance of the resin, so that the film forming performance and strength of the resin are further improved, and the preparation method is suitable for wide popularization of the glass fiber film forming agent industry.

Detailed Description

So that the technical features and content of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.

< test method >

The solid content testing method comprises the following steps: and (3) taking a proper amount of aqueous polyurethane-polyurea dispersoid to be measured in a container made of tinfoil paper, weighing the weight change before and after the water-based polyurethane-polyurea dispersoid is placed at 150 ℃ for 20 minutes, and calculating the solid content of the water-based polyurethane-polyurea dispersoid.

Particle size testing method: measuring the particle size and the particle size distribution of a sample to be measured by Dynamic Light Scattering (DLS); particle size and particle size distribution of the aqueous polyurethane-polyurea dispersion were measured in a particle sizer of Zetasizer Nano ZS from malvern, test temperature 25 ℃, laser angle 90 °, test laser wavelength 633nm.

The pH value test method comprises the following steps: the test was performed using a pH meter.

The viscosity test method comprises the following steps: the test was performed using a BROOKFIELD viscometer, rotor No. 3/30 rpm.

Test method of thermal weight loss (TGA): according to ISO11358 plastics-thermal weight loss method, adopting TGA/DSC < 3+ > of Metretolterodine, and heating at the temperature of 30-600 ℃ at the rate of: 10 ℃/min, the gas is: nitrogen, flow: 50 ml/min; the experimental result can obtain a temperature-weight loss ratio curve, and the higher the non-decomposition ratio (weight loss ratio) is at the same temperature, the better the thermal weight loss effect is.

The appearance color testing method comprises the following steps: and observing by naked eyes.

The mechanical property testing method comprises the following steps: according to GB/T1040 92 standard, according to the condition of a sample to be tested, a tensile test can be performed at a tensile speed of 50mm/min and at room temperature, and a stress-strain curve of the sample to be tested can be obtained according to test results, and data such as tensile strength, elongation at break, modulus and the like of the material can be obtained from the curve.

Testing the compounding stability of the cationic auxiliary agent: weighing 20g of aqueous polyurethane-polyurea dispersoid resin emulsion to be measured, adding 1g of hexadecyl trimethyl ammonium bromide with the concentration of 20%, mixing, stirring for 30min under the condition of 300 r/min, uniformly mixing, filtering, and finding that the slag condition is optimal without generating slag.

High temperature yellowing resistance test: pouring the aqueous polyurethane-polyurea dispersoid resin emulsion to be tested on a film forming plate, drying for 8 hours at 50 ℃, continuously drying for 4 hours at 80 ℃, heating for 1 hour at 210 ℃, and evaluating the color change grade according to national standard GB/T1766-1995; visual inspection of yellowing results: when the visual inspection is 'no color change', the corresponding color difference value is less than or equal to 1.5, when the visual inspection is 'very slight color change', the corresponding color difference value ranges from 1.6 to 3.0, when the visual inspection is 'slight color change', the corresponding color difference value ranges from 3.1 to 6.0, and when the visual inspection is 'obvious color change', the corresponding color difference value ranges from 6.1 to 9.0.

Solvent resistance test: pouring the aqueous polyurethane-polyurea dispersoid resin emulsion to be tested on a film forming plate, drying for 8 hours at 50 ℃, and continuously drying for 4 hours at 80 ℃ to obtain an aqueous polyurethane adhesive film; the method comprises the steps of weighing a certain mass (about 1 g) of aqueous polyurethane adhesive film m1, putting into 100ml of acetone, sealing and soaking for 24 hours, taking out the adhesive film, drying for 4 hours at 80 ℃, weighing the mass of the adhesive film m2, wherein the ratio of the mass of the adhesive film m2 to the mass of the original adhesive film m1 is used as a solvent resistance reference (0-100%), and the solvent resistance is better when the ratio is higher.

The hydroxyl number content is the theoretical hydroxyl number, calculated on the basis of the functionality of the component S7) added.

Thermal storage stability test: the sample to be measured is placed in a constant temperature oven at 50 ℃ and placed for one month, and whether layering exists on the appearance of the emulsion is observed.

< source of raw materials >

Component S1):

HDI, (hexamethylene diisocyanate, having an NCO content of about 50.0 wt%) available from vancomic chemical group limited;

IPDI, (isophorone diisocyanate, having an NCO content of about 37.8 wt%) available from bayer, germany;

component S2):

CMA654, (poly (neopentyl glycol adipate) -1, 6-hexanediol ester diol having a number average molecular weight=1500 and a functionality of 2), available from katsumadai university chemistry;

PNA2000, (poly (neopentyl glycol adipate) glycol having a number average molecular weight=2000 and a functionality of 2), available from katskuwa chemistry;

PTMEG2000, (polytetrahydrofuran ether glycol, number average molecular weight=2000, functionality 2), available from basf;

component S3):

Ymer ^TM n120 (having a hydroxyl number of 112mgKOH/g, number average molecular weight=1200, functionality of 2), purchased from buston;

component S4):

NPG (neopentyl glycol) purchased from Wanhua chemical group Co., ltd;

component S5):

a95 (sodium ethylenediamine ethanesulfonate), purchased from catalpol;

component S6):

IPDA (isophorone diamine), available from bayer, germany;

hydroxyethyl ethylenediamine available from jenan, yofeng, chemical industry;

component S7):

tris (Tris) aminomethane), purchased from aladine;

acetone, wanhua chemical group Co., ltd;

BiCat8108 (bismuth-based catalyst), available from the united states leading.

Cetyl trimethylammonium bromide, available from alaa Ding Shiji.

Since the NCO groups of the system are excessive and the reactivity is high in the reaction, it is considered that the molar ratio (i.e., R value) of isocyanate groups and polyol hydroxyl groups in the final product is very close to the raw material feed ratio. Thus, the molar ratio (i.e., R value) of isocyanate groups to polyol hydroxyl groups in the following examples and comparative examples was calculated according to the feed ratio of the raw material diisocyanate to the polymer polyol.

Example 1:

(1) Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 37.84g

HDI、50g IPDI，23g Ymer ^TM N120, 240g PNA2000, 16.4g neopentyl glycol, 0.12g BiCat8108 and 37g acetone, stirring and heating to 80 ℃ to react for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating isocyanate-terminated prepolymer;

(2) Then cooling the system to about 50-56 ℃, adding 550g of acetone, uniformly stirring, maintaining the temperature between 40-45 ℃, and dissolving and diluting the materials in the system to obtain diluted isocyanate-terminated prepolymer;

(3) Dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.6g of A95 in 40g of water, fully and uniformly stirring to obtain an aqueous solution, adding the aqueous solution into the diluted isocyanate-terminated prepolymer obtained in the step (2) within 1-3 minutes, and maintaining the system at 45-50 ℃ for chain extension reaction for 25 minutes; pouring the prepolymer prepared by the chain extension reaction into a dispersing cup, and adding 433g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

(4) Adding an aqueous solution containing Tris (which is an aqueous solution prepared by adding 10g of Tris and 40g of water) prepared in advance into a dispersing cup after dispersing is finished, and performing end-capping reaction for 8-10 minutes to obtain a coarse emulsion containing aqueous polyurethane-polyurea;

The crude emulsion was desolventized by distillation under reduced pressure to remove acetone therein, thereby obtaining a milky-white, bluish-blue-light aqueous polyurethane-polyurea dispersion resin emulsion having a solid content of 50wt% and a particle size of 346nm.

Example 2:

HDI、50g IPDI，23g Ymer ^TM N120, 240g PTMEG2000, 16.4g neopentyl glycol, 0.12g BiCat8108 and 37g acetone, stirringStirring and heating to 80 ℃ to react for 3 hours until NCO in the system basically reaches or approaches to a theoretical value, so as to generate isocyanate-terminated prepolymer;

the crude emulsion is desolventized by a reduced pressure distillation mode, and acetone in the crude emulsion is removed to obtain milky-white and faint blue-light aqueous polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50wt%, and the particle size of the emulsion is 298nm.

Example 3:

HDI、50g IPDI，23g Ymer ^TM N120, 240g of CMA654, 12g of neopentyl glycol, 0.12g of BiCat8108 and 37g of acetone, stirring and heating to 80 ℃ to react for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating isocyanate-terminated prepolymer;

(3) Dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.6g of A95 in 40g of water, fully and uniformly stirring to obtain an aqueous solution, adding the aqueous solution into the diluted isocyanate-terminated prepolymer obtained in the step (2) within 1-3 minutes, and maintaining the system at 45-50 ℃ for chain extension reaction for 25 minutes; pouring the prepolymer prepared by the chain extension reaction into a dispersing cup, and adding 428g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

the crude emulsion is desolventized by a reduced pressure distillation mode, and acetone in the crude emulsion is removed to obtain milky-white and faint blue-light aqueous polyurethane-polyurea dispersoid resin emulsion, wherein the solid content of the emulsion is 50wt% and the particle size of the emulsion is 315nm.

Example 4:

HDI、50g IPDI，18g Ymer ^TM N120, 146g of CMA654, 19.6g of neopentyl glycol, 0.08g of BiCat8108 and 27g of acetone, stirring and heating to 80 ℃ to react for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating isocyanate-terminated prepolymer;

(2) Then cooling the system to about 50-56 ℃, adding 400g of acetone, uniformly stirring, maintaining the temperature between 40-45 ℃, and dissolving and diluting the materials in the system to obtain diluted isocyanate-terminated prepolymer;

(3) Dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.2g of A95 in 40g of water, fully and uniformly stirring to obtain an aqueous solution, adding the aqueous solution into the diluted isocyanate-terminated prepolymer obtained in the step (2) within 1-3 minutes, and maintaining the system at 45-50 ℃ for chain extension reaction for 25 minutes; pouring the prepolymer prepared by the chain extension reaction into a dispersing cup, and adding 312g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

the crude emulsion is desolventized by a reduced pressure distillation mode, and acetone in the crude emulsion is removed to obtain milky-white and faint blue-light aqueous polyurethane-polyurea dispersoid resin emulsion, wherein the solid content of the emulsion is 50wt%, and the particle size of the emulsion is 328nm.

Example 5:

HDI、50g IPDI，33g Ymer ^TM N120, 225g CMA654, 12g neopentyl glycol, 0.2g BiCat8108 and 52g acetone, stirring and heating to 80 ℃ to react for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating isocyanate-terminated prepolymer;

(2) Then cooling the system to about 50-56 ℃, adding 536g of acetone, uniformly stirring, maintaining the temperature between 40-45 ℃, and dissolving and diluting the materials in the system to obtain diluted isocyanate-terminated prepolymer;

(3) Dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.6g of A95 in 42g of water, fully and uniformly stirring to obtain an aqueous solution, adding the aqueous solution into the diluted isocyanate-terminated prepolymer obtained in the step (2) within 1-3 minutes, and maintaining the system at 45-50 ℃ for chain extension reaction for 25 minutes; pouring the prepolymer prepared by the chain extension reaction into a dispersing cup, and adding 410g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

(4) Adding an aqueous solution containing Tris (which is an aqueous solution prepared by adding 11g of Tris and 48g of water) prepared in advance into a dispersing cup after dispersing is finished, and performing end-capping reaction for 8-10 minutes to obtain a coarse emulsion containing aqueous polyurethane-polyurea;

the crude emulsion is desolventized by a reduced pressure distillation mode, and acetone in the crude emulsion is removed to obtain milky-white and faint blue-light aqueous polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50wt% and the particle size of the emulsion is 305nm.

Example 6:

(4) Adding an aqueous solution containing Tris (which is an aqueous solution prepared by adding 4g of Tris and 16g of water) prepared in advance into a dispersing cup after dispersing is finished, and performing end-capping reaction for 8-10 minutes to obtain a coarse emulsion containing aqueous polyurethane-polyurea;

the crude emulsion is desolventized by a reduced pressure distillation mode, and acetone in the crude emulsion is removed to obtain the milky-white and faint blue-light aqueous polyurethane-polyurea dispersoid resin emulsion, wherein the solid content of the emulsion is 50wt%, and the particle size of the emulsion is 321nm.

Example 7:

(1) To a reflux condenser tube,Into a four-necked flask equipped with a thermometer and mechanical stirring, 37.84g of the flask were charged

(4) Adding an aqueous solution containing Tris (which is an aqueous solution prepared by adding 19.5g of Tris and 80g of water) prepared in advance into a dispersing cup after dispersing, and carrying out end-capping reaction for 8-10 minutes to obtain a crude emulsion containing aqueous polyurethane-polyurea;

the crude emulsion is desolventized by a reduced pressure distillation mode, and acetone in the crude emulsion is removed to obtain milky-white and faint blue-light aqueous polyurethane-polyurea dispersoid resin emulsion, wherein the solid content of the emulsion is 50wt%, and the particle size of the emulsion is 286nm.

Comparative example 1:

HDI、50g IPDI，5.3g Ymer ^TM N120, 240g CMA654, 14g neopentyl glycol, 0.11g BiCat8108 and 35g acetone, and the mixture is stirred and heated to 80 ℃ for 3h of reaction untilThe NCO in the system basically reaches or approaches to a theoretical value to generate isocyanate-terminated prepolymer;

(2) Then cooling the system to about 50-56 ℃, adding 524g of acetone, uniformly stirring, maintaining the temperature between 40-45 ℃, and dissolving and diluting the materials in the system to obtain diluted isocyanate-terminated prepolymer;

(3) Dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 9g of A95 in 68g of water, fully and uniformly stirring to obtain an aqueous solution, adding the aqueous solution into the diluted isocyanate-terminated prepolymer obtained in the step (2) within 1-3 minutes, and maintaining the system at 45-50 ℃ for chain extension reaction for 25 minutes; pouring the prepolymer prepared by the chain extension reaction into a dispersing cup, and adding 372g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

(5) The crude emulsion is desolventized by reduced pressure distillation to remove acetone therein, thus obtaining milky blue-light aqueous polyurethane-polyurea dispersoid resin emulsion with the solid content of 50wt% and the particle size of 256nm.

Comparative example 2:

HDI、50gIPDI，23g Ymer ^TM N120, 240g of CMA654, 12g of neopentyl glycol, 0.12g of BiCat8108 and 37g of acetone, stirring and heating to 80 ℃ to react for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating isocyanate-terminated prepolymer;

(3) Dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.6g of A95 in 40g of water, fully and uniformly stirring to obtain an aqueous solution, adding the aqueous solution into the diluted isocyanate-terminated prepolymer obtained in the step (2) within 1-3 minutes, and maintaining the system at 45-50 ℃ for chain extension reaction for 25 minutes; pouring the prepolymer prepared by the chain extension reaction into a dispersing cup, and adding 420g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing to obtain a coarse emulsion containing aqueous polyurethane-polyurea;

Comparative example 3:

(3) Dissolving 4g of IPDA, 2g of hydroxyethyl ethylenediamine and 1.6g of A95 in 40g of water, fully and uniformly stirring to obtain an aqueous solution, adding the aqueous solution into the diluted isocyanate-terminated prepolymer obtained in the step (2) within 1-3 minutes, and maintaining the system at 45-50 ℃ for chain extension reaction for 25 minutes; pouring the prepolymer prepared by the chain extension reaction into a dispersing cup, and adding 428g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

(4) Adding an aqueous solution containing Tris (which is an aqueous solution prepared by adding 26g of Tris and 104g of water) prepared in advance into a dispersing cup after dispersing is finished, and performing end-capping reaction for 8-10 minutes to obtain a coarse emulsion containing aqueous polyurethane-polyurea;

the crude emulsion is desolventized by a reduced pressure distillation mode, and acetone in the crude emulsion is removed to obtain the milky-white and faint blue-light aqueous polyurethane-polyurea dispersoid resin emulsion, wherein the solid content of the emulsion is 50wt%, and the particle size of the emulsion is 281nm.

Comparative example 4:

HDI、50g IPDI，33g Ymer ^TM N120, 400g CMA654,0.2g BiCat8108 and 52g of acetone are stirred and heated to 80 ℃ to react for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and an isocyanate-terminated prepolymer is generated;

(2) Then cooling the system to about 50-56 ℃, adding 782g of acetone, uniformly stirring, maintaining the temperature between 40-45 ℃, and dissolving and diluting the materials in the system to obtain diluted isocyanate-terminated prepolymer;

(3) Dissolving 3.8g of IPDA, 3.8g of hydroxyethyl ethylenediamine and 2.4g of A95 in 42g of water, fully and uniformly stirring to obtain an aqueous solution, adding the aqueous solution into the diluted isocyanate-terminated prepolymer obtained in the step (2) within 1-3 minutes, and maintaining the system at 45-50 ℃ for chain extension reaction for 25 minutes; pouring the prepolymer prepared by the chain extension reaction into a dispersing cup, and adding 620g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

(4) Adding an aqueous solution containing Tris (which is an aqueous solution prepared by adding 12g of Tris and 48g of water) prepared in advance into a dispersing cup after dispersing is finished, and performing end-capping reaction for 8-10 minutes to obtain a coarse emulsion containing aqueous polyurethane-polyurea;

the crude emulsion is desolventized by a reduced pressure distillation mode, and acetone in the crude emulsion is removed to obtain milky-white and faint blue-light aqueous polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50wt%, and the particle size of the emulsion is 317nm.

The performance indexes of the aqueous polyurethane resins prepared in each of the examples and comparative examples are shown in the following tables 1 to 3:

TABLE 1 Performance index of aqueous polyurethane-polyurea dispersion resins

From the experimental data in table 1, it can be seen that: compared with polyester polyol, because the cohesion energy of polyether polyol is low, ether bond is easy to rotate and ether bond is easy to break at high temperature, the comprehensive performance of the resin prepared by selecting polyester polyol as component S2) in the formula system of the aqueous polyurethane-polyurea dispersion resin is better than that prepared by selecting polyether polyol as component S2).

TABLE 2 Performance index of aqueous polyurethane-polyurea dispersion resins

As can be seen from the experimental data of table 2:

the aqueous polyurethane-polyurea dispersion resin prepared by the technical scheme has excellent comprehensive performance; example 3 as a preferred embodiment, the properties of the resulting resin can achieve better results and overall performance improvements.

The thermal weightlessness of the product can be affected by weakening the microphase separation degree by adjusting the different soft and hard segment ratios (i.e., the ratio of the components S1/S2). The comparison of the test results of examples 3-5 shows that the optimum soft and hard segment proportion (the proportion of the components S1/S2) is designed to enable the microphase separation degree to reach an optimum state, so that the film forming property can be improved, and the aqueous polyurethane-polyurea dispersion resin can have high thermal weight loss rate at high temperature under the condition of ensuring the mechanical property.

By comparing the test results of the example 3 with the test results of the examples 6-7, the proper end-capping rate can ensure the high molecular weight, gao Niaoji and high active functional group content of the resin when the component S7) is added into the system for end-capping reaction, so that the resin has excellent performance; in addition, the resin can be fully cured and crosslinked with a curing agent on the premise of ensuring the excellent performance of the obtained resin, so that the film forming performance and mechanical strength of the resin are further improved.

TABLE 3 Performance index of aqueous polyurethane-polyurea dispersion resins

From the experimental data in table 3, it can be seen that:

as can be seen from the comparison of the example 3 and the comparative example 1, the composition of the application adopts the nonionic hydrophilic group as a hydrophilic main body, and the anionic group-containing component is an auxiliary hydrophilic body, so that the compounding stability of the obtained polyurethane-polyurea resin and cations can be better improved. In comparative example 1, the polyurethane resin prepared by taking the component containing the anionic group as a hydrophilic main body (the dosage of the component S3 is reduced and the dosage of the component S5 is increased) is gelled in the compounding process with the cationic auxiliary agent, which indicates that the compound emulsion formed by the main anionic resin and other cationic auxiliary agents cannot exist stably when the main anionic resin is used for impregnating the glass fiber into the film forming agent; in addition, the resulting resin also has poor high temperature yellowing resistance. The cationic stability and the high-temperature yellowing resistance of the dispersion resin with the nonionic hydrophilic group serving as a hydrophilic main body and the anionic group-containing component serving as an auxiliary hydrophilic body are better.

As can be seen from a comparison of example 3 and comparative example 2, if the end-capping treatment is carried out without adding component S7) to the system, the overall properties of the resulting resin are reduced, in particular in high Wen Naihuang denaturation; at the same time, the mechanical properties, solvent resistance and thermal weight loss are all inferior to those of the product obtained in example 3.

As can be seen from a comparison of example 3 and comparative example 3, if the amount of component S7) in the system is too large, an excessively high end-capping rate will affect the storage stability of the emulsion at high temperatures. In comparative example 3, too high a capping rate, the hydrophilic effect of the excessive hydroxyl groups introduced would thicken the system, resulting in an increase in the initial viscosity of the system and eventually a deterioration in the thermal storage stability of the resin.

As can be seen from a comparison of example 3 and comparative example 4, if the proportions of components S1 and S2 of the formulation are too low, the mechanical properties, thermal weight loss and solvent resistance of the resulting resin are adversely affected; meanwhile, the molecular weight of the resin is too large because of the large proportion of the soft segment, so that the initial viscosity of the system is increased, and finally the thermal storage stability of the resin is deteriorated.

In conclusion, the aqueous polyurethane-polyurea dispersion resin can maintain good compoundability with other cationic components in the impregnating compound, and ensures high stability of the paint emulsion; meanwhile, the polyurethane can obtain higher strength and mechanical property, has excellent high-temperature yellowing resistance and high thermal weight loss retention rate, has better solvent resistance than the traditional waterborne polyurethane, and has larger practical use value.

The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the spirit of the invention.

Claims

1. The aqueous polyurethane-polyurea dispersion resin is characterized by being prepared from the following raw materials by reaction:

s1) at least one diisocyanate;

s2) at least one polymer polyol having an average molecular weight of 500-3000g/mol;

wherein the molar ratio of component S1) to component S2) is from 2:1 to 5:1;

s3) at least one nonionic hydrophilic compound having an average molecular weight of 300-2000g/mol;

s6) at least one amine small molecule chain extender containing active hydrogen; the molecular weight of the amine small molecular chain extender containing active hydrogen is 30-200g/mol;

s7) at least one monoamine small molecule end-capping agent containing active hydrogen, wherein the molecular weight of the monoamine small molecule end-capping agent is 30-300g/mol, and the monoamine small molecule end-capping agent is selected from the group consisting of tris (hydroxymethyl) aminomethane;

The weight sum of the components is taken as the reference, and the dosage of each component is as follows:

the amount of component S1) is 10-45wt%;

the amount of component S2) is 45-75wt%;

the amount of component S3) is 3-10wt%;

the amount of component S4) is 0 to 10% by weight;

the amount of component S5) is 0.1 to 1 wt.%;

the amount of component S6) is 0.5 to 5 wt.%;

the amount of component S7) is 1 to 5% by weight.

2. The aqueous polyurethane-polyurea dispersion resin according to claim 1, wherein the amounts of the components, based on the sum of the weights of the components, are as follows:

the amount of component S1) is 15-25 wt.%;

the amount of component S2) is 55-70 wt.%;

the amount of component S3) is 5-8wt%;

the amount of component S4) is 2-8 wt.%;

the amount of component S5) is 0.2 to 0.8 wt.%;

the amount of component S6) is 1-4 wt.%;

the amount of component S7) is 2 to 3% by weight.

3. The aqueous polyurethane-polyurea dispersion resin according to claim 1, wherein the molar ratio of component S1) to component S2) is from 2.5:1 to 4:1.

4. The aqueous polyurethane-polyurea dispersion resin according to claim 1, wherein the nonionic hydrophilic compound is a monohydric alcohol and/or a dihydric alcohol having a polyethylene oxide segment in the main chain and/or the side chain.

5. The aqueous polyurethane-polyurea dispersion resin according to claim 1, wherein the nonionic hydrophilic compound has an average molecular weight of 500 to 1500g/mol.

6. The aqueous polyurethane-polyurea dispersion resin according to claim 1, wherein the amine-based small molecule chain extender containing an active hydrogen is a diamine-based small molecule chain extender containing an active hydrogen and/or a hydrazine-based small molecule chain extender containing an active hydrogen.

7. The aqueous polyurethane-polyurea dispersion resin according to claim 1, wherein component S1) is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate; and/or

The component S2) is selected from one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, polycarbonate glycol, polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, neopentyl glycol adipate glycol, 1, 6-hexanediol adipate glycol and 1, 6-hexanediol adipate glycol; and/or

The polymerized units of component S3) contain ethylene oxide in a proportion of 90 to 100% by weight relative to the total weight of the nonionic hydrophilic compound; the nonionic hydrophilic compound is selected from polyethylene oxide ether glycol and/or polyethylene glycol methyl ether; and/or

The component S4) is selected from one or more of 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, neopentyl glycol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol; and/or

The component S5) is selected from one or more of sodium ethylenediamine ethanesulfonate, sodium 2- (2-aminoethyl) aminopropanesulfonate, sodium 1, 4-butanediol-2-sulfonate and sodium 1, 2-dihydroxy-3-propanesulfonate; and/or

The component S6) is one or more selected from ethylenediamine, hydroxyethyl ethylenediamine, hexamethylenediamine, pentamethylenediamine, diethylenetriamine, isophoronediamine and 4, 4-diphenyl methane diamine.

8. The aqueous polyurethane-polyurea dispersion resin according to claim 7, wherein component S1) is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate; and/or

Component S2) is poly (neopentyl glycol adipate) -1, 6-hexanediol ester diol; and/or

Component S3) is selected from polyethylene oxide ether glycols; and/or

The component S4) is selected from one or more of 1, 4-butanediol, 1, 6-hexanediol and neopentyl glycol; and/or

The component S5) is sodium ethylenediamine-based ethanesulfonate; and/or

Component S6) is selected from hydroxyethylethylenediamine and/or isophoronediamine.

9. The aqueous polyurethane-polyurea dispersion resin according to any one of claims 1 to 8, wherein said raw materials further comprise, based on the total weight of components S1) -S7):

water in an amount of 100 to 250 wt.% based on the total weight of components S1) to S7);

a low boiling point organic solvent added in an amount of 1.2 to 2 times the total weight of the components S1) to S7); the low boiling point organic solvent is selected from acetone and/or butanone;

a catalyst added in an amount of 0.01 to 0.05wt% based on the total weight of the components S1) to S7); the catalyst is selected from dibutyl tin dilaurate, cobaltous octoate or BiCat8108.

10. The aqueous polyurethane-polyurea dispersion resin according to claim 9, wherein the amount of water added is 150 to 200wt% based on the total weight of component S1) -component S7);

the low-boiling point organic solvent is acetone;

the addition amount of the catalyst is 0.02-0.03wt% of the total weight of the components S1) -S7); the catalyst is BiCat8108.

11. A process for the preparation of an aqueous polyurethane-polyurea dispersion resin as claimed in any one of claims 1 to 10, comprising the steps of:

(1) Uniformly mixing the component S1), the component S2), the component S3), the component S4), the catalyst and the low-boiling point organic solvent to react until NCO in the system approaches a theoretical value, and generating isocyanate-terminated prepolymer;

(4) Adding an aqueous solution containing the component S7) into the reaction system of the step (3) to carry out end-capping reaction to obtain a coarse emulsion containing polyurethane-polyurea;

optionally, the low-boiling point organic solvent is partially or completely removed by reduced pressure distillation, and the aqueous polyurethane-polyurea dispersion resin is obtained.

12. The method of claim 11, wherein the aqueous polyurethane-polyurea dispersion resin has a solids content of 40-60%;

The average particle size of the aqueous polyurethane-polyurea dispersion resin is 200-600nm.

13. The method of claim 12, wherein the aqueous polyurethane-polyurea dispersion resin has a solids content of 45-55%;

the average particle size of the aqueous polyurethane-polyurea dispersion resin is 300-500nm.

14. The method of claim 11, wherein the temperature of the reaction in step (1) is 70-80 ℃;

the process conditions of dissolution dilution in the step (2) comprise: the dissolution temperature is 40-50 ℃ and the dissolution time is 5-10min;

in the aqueous solution containing the component S5) and the component S6) in the step (3), the water is used in an amount which is 4-6 times of the sum of the mass of the component S5) and the mass of the component S6); the technological conditions of the chain extension reaction comprise: the reaction temperature is 40-50 ℃ and the reaction time is 15-25min;

in the aqueous solution containing the component S7) in the step (4), the water dosage is 4-6 times of the mass of the component S7); the reaction time of the end capping reaction is 8-10min.

15. Use of an aqueous polyurethane-polyurea dispersion resin for the preparation of a glass fiber-wetting film former, characterized in that the aqueous polyurethane-polyurea dispersion resin is prepared according to any one of claims 1 to 10 or according to any one of claims 11 to 14.

16. The use according to claim 15, wherein the aqueous polyurethane-polyurea dispersion resin is compounded with a cationic auxiliary agent during the preparation of the glass fiber-infiltrating film-forming agent;

the cation auxiliary agent is selected from one or more of dimethyl allyl ammonium chloride, calcium sulfate and cetyl trimethyl ammonium bromide.

17. Use according to claim 16, characterized in that the cationic auxiliary is cetyltrimethylammonium bromide.