CN113861377A

CN113861377A - Waterborne polyurethane-polyurea dispersion resin and preparation method and application thereof

Info

Publication number: CN113861377A
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: 2021-12-31
Anticipated expiration: 2040-06-30
Also published as: CN113861377B

Abstract

The invention belongs to the technical field of glass fiber soaking film-forming agents, and particularly relates to waterborne polyurethane-polyurea dispersion resin and a preparation method and application thereof, wherein the resin is prepared by reacting the following raw materials: s1) diisocyanate; s2) a polymer polyol; s3) non-ionic hydrophilic compounds; s4) a polyol micromolecule chain extender containing active hydrogen, wherein the molecular weight is 30-200 g/mol; s5) sulfonic acid type hydrophilic chain extender containing active hydrogen; s6) an amine micromolecule chain extender containing active hydrogen, wherein the molecular weight is 30-200 g/mol; s7) monoamine small molecule blocking agent containing active hydrogen, and the molecular weight is 30-300 g/mol. The waterborne polyurethane-polyurea dispersion resin disclosed by the invention can keep good compounding stability with a cationic component in a sizing agent, and has excellent mechanical property, high-temperature yellowing resistance and solvent resistance and better thermal weight loss property.

Description

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

Technical Field

The invention belongs to the technical field of glass fiber soaking film forming agents, and particularly relates to an aqueous 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 the fields of transportation, clothing, construction, textile, synthetic leather and the like. The waterborne polyurethane is taken as a branch of polyurethane resin, so that the waterborne polyurethane has excellent performance, high strength after film forming, and good toughness and elasticity; when the glass fiber sizing agent is applied to the field of glass fiber sizing treatment, the glass fiber sizing agent has excellent bonding property and film forming property, can effectively protect glass fibers, has strong polarity, can be well combined with most matrix resins, can well solve the problem of non-ideal interface combination, and can be used as a main film forming agent component of an enhanced glass fiber sizing agent. However, when the glass fiber sizing agent is compounded, a large amount of anion auxiliary agent and cation auxiliary agent can be added into a formula system, and the compounding stability of the resin is challenged. The traditional ionic waterborne polyurethane can not meet the industrial requirements, and domestic glass fiber infiltration film forming agents containing the waterborne polyurethane depend on import and are expensive. Therefore, some researches and researches on the waterborne polyurethane film forming agent for the glass fiber have appeared.

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 dispersed in water after neutralization to prepare the waterborne polyurethane film-forming agent, although the method mentioned in the text is excellent in resin film-forming property and good in emulsion storage stability, when the waterborne polyurethane film-forming agent is used as a film-forming agent in a glass fiber sizing agent, the emulsion is severely thickened and even demulsified due to the compounding of the emulsion and other cationic components contained in the film-forming agent, so that the stability of the compound is poor; in addition, an organic solvent and a neutralizing agent are also introduced in the synthesis process, so that the VOC content is high, the current environment-friendly trend is not facilitated, and the industrial requirements are difficult to meet.

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 a glass fiber film forming agent by adding an active functional group to perform a ring opening reaction with an epoxy group, so that the glass fiber film forming agent has good stiffness and bundling property; however, the added epoxy resin has poor stability, is very unstable in a polyurethane modified resin system, and is easy to settle and delaminate; and because 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 synthetic process to dilute the epoxy, so that the method is contrary to the development trend of the existing industry, and the comprehensive cost performance is not high.

Therefore, the waterborne polyurethane resin which has excellent comprehensive performance and simultaneously has the idea of environmental protection and green is more and more favored by people. However, when the traditional waterborne polyurethane resin is used as a film forming agent, because the proportion of the active ingredients of the waterborne polyurethane resin in the impregnating solution is low, the number of functional groups capable of reacting 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 additives in the impregnating solution is also a technical problem to be solved. Therefore, when the traditional waterborne polyurethane resin is used as a film forming agent, the comprehensive performance is poor, the strength is low, and the processing and use requirements of glass fibers cannot be met. In conclusion, the development of the waterborne polyurethane resin with excellent performance and excellent ion stability during compounding becomes the focus of the research in the field of the waterborne glass fiber at present.

Disclosure of Invention

The invention aims to provide the waterborne polyurethane-polyurea dispersion resin and the preparation method and application thereof aiming at the problems of the existing film forming agent for the glass fiber, the waterborne polyurethane-polyurea dispersion resin has higher formula stability, can keep good compounding stability with other cationic components in an impregnating compound when being used for a glass fiber film forming agent, ensures high stability of paint preparation emulsion, can obtain higher strength and mechanical property, has excellent high-temperature yellowing resistance and solvent resistance, has better thermal weight loss, and can meet the high-temperature process requirement in the glass fiber processing process.

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

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

s1) at least one diisocyanate;

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

wherein the molar ratio of component S1) to component S2) is 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 2.5:1 to 4: 1;

s3) at least one non-ionic hydrophilic compound with an average molecular weight of 300-2000g/mol, preferably 500-1500 g/mol; the nonionic hydrophilic compound is preferably a monohydric alcohol and/or a dihydric alcohol, the main chain and/or the side chain of which contains polyoxyethylene chain segments;

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

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

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

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

According to the present invention, there is provided an aqueous polyurethane-polyurea dispersion resin, wherein the main structural formula of the aqueous polyurethane-polyurea dispersion resin can be represented by formula I:

in the formula (I), the compound is shown in the specification,

R₁can be selected from

R₂Can be selected from

R₃Can be selected from

Wherein m is 3-8 (for example, n is 4, 5, 6, 7);

the value of n is 10 to 20 (for example, n is 12, 14, 16, 18).

According to the aqueous polyurethane-polyurea dispersion resin provided by the present invention, in some examples, the components are used in the following amounts based on the sum of the weights of the components (for example, 100 wt%):

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

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

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

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

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

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

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

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, poly 1, 4-butanediol adipate diol, poly neopentyl glycol adipate diol, poly 1, 6-hexanediol adipate diol, and poly neopentyl glycol-1, 6-hexanediol adipate diol, preferably poly neopentyl glycol-1, 6-hexanediol adipate diol (e.g., CMA 654).

In some examples, the polymerized units (containing polyethylene oxide segments) of component S3) contain ethylene oxide in a proportion of 90-100 wt% of the total weight of the non-ionic hydrophilic compound; preferably, the non-ionic 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 of Tego Chemie

D-3403, Ymer by Perstrop^TMN120 and one or more of MPEG1200 of Letian, Korea, preferably Ymer of Perstrop^TMN120And/or MPEG1200 of museum corporation, korea.

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 adjusted primarily according to the molar ratio (i.e., the level of R value) of component S1) to component S2).

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

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

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

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

water, added in an amount of 100-250 wt%, preferably 150-200 wt%, of the total weight of the component S1) -the component S7);

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

a catalyst added in an amount of 0.01 to 0.05 wt% (e.g., 0.015 wt%, 0.025 wt%, 0.035 wt%, 0.045 wt%), preferably 0.02 to 0.03 wt%, based on the total weight of the component S1) to the component S7); in some examples, the catalyst is selected from dibutyltin dilaurate, cobaltous octoate, or BiCat8108, preferably BiCat 8108.

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 a component S1), a component S2), a component S3) and a component S4), a catalyst and a low-boiling-point organic solvent for reaction until NCO in a system basically reaches or approaches a theoretical value to generate an 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 a component S5) and a component S6) into the reaction system in the step (2), carrying out chain extension reaction, and adding water for shearing and dispersing;

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

Optionally, the low-boiling organic solvent is partially or completely removed by distillation under reduced pressure to obtain the aqueous polyurethane-polyurea dispersion resin. The processing equipment and processing techniques for the 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 200-600nm, preferably 300-500 nm.

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 for dilution by dissolution in step (2) include: the dissolving temperature is 40-50 deg.C (e.g. 45 deg.C), and the dissolving time is 5-10min (e.g. 6min, 8 min).

In some examples, in the aqueous solution containing the component S5) and the component S6) in the step (3), the amount of water is 4 to 6 times (e.g., 5 times) the sum of the masses of the component S5) and the component S6). The aqueous solution containing the component S5) and the component S6) may be an aqueous solution prepared from 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 40-50 deg.C (e.g., 45 deg.C), and the reaction time is 15-25min (e.g., 20 min).

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

The invention also provides an application of the waterborne polyurethane-polyurea dispersion resin in preparing a glass fiber soaking film forming agent, and the waterborne 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 soaking film forming agent, the waterborne polyurethane-polyurea dispersion resin is compounded with a cationic auxiliary agent. The dosage of the cationic auxiliary agent can be determined according to the use requirement of the glass fiber soaking film forming agent.

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

According to the invention, by introducing the nonionic hydrophilic compound component and taking the nonionic hydrophilic compound component as the hydrophilic main body in the waterborne polyurethane-polyurea resin and simultaneously adjusting the dosage of the added ionic hydrophilic compound (such as the sulfonic acid type hydrophilic chain extender), when the obtained dispersion resin is applied to the glass fiber soaking film forming agent, a compound system formed by the resin and the cationic assistant can be stabilized, and the excellent stability of the compound system is ensured.

In the preparation process of the resin, by designing the adding amount ratio of each component, chain extension can be carried out under the condition of high carbamido content and the chain extension ratio is adjusted to obtain a polyurethane resin chain segment with large molecular weight, so that 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 waterborne polyurethane resin, the high-hydroxyl content can be realized under the condition of ensuring that the resin has large molecular weight by introducing a high-functionality end capping group into a system, and the problems of poor performance and the like of the resin after subsequent curing due to low initial molecular weight are solved.

The system for preparing the aqueous polyurethane-polyurea dispersion is a system with excessive NCO, the dosage of the component S7) needs to be controlled, the excessive dosage can cause the blocking rate to be higher, the molecular weight of the obtained polyurethane chain segment is smaller, and the excessive NCO blocked can not be further extended with water to increase the molecular weight, thereby affecting the performance of the product.

Therefore, the waterborne polyurethane-polyurea resin obtained by the invention has excellent ionic stability and can meet the compounding requirement of being used as a glass fiber soaking film-forming agent; meanwhile, the waterborne polyurethane-polyurea resin has higher strength and mechanical property, excellent high-temperature yellowing resistance and solvent resistance, and better thermal weight loss property, and can meet the high-temperature process requirement in the glass fiber processing process.

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

(1) because the special proportion of soft and hard segments (the proportion of the components S1/S2, namely the R value) is designed by the formula, the microphase separation degree of the waterborne polyurethane-polyurea dispersion resin can reach an optimal state, the prepared waterborne polyurethane-polyurea dispersion resin has excellent film forming property and solvent resistance, the thermal weight loss rate of the waterborne polyurethane-polyurea dispersion resin can deviate towards the high-temperature direction, and the thermal weight loss requirement of the glass fiber processing process at the temperature of 300-;

(2) the hydrophilic compound component (component S3) containing nonionic groups is introduced in the synthesis process of the waterborne 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 that a small amount of sulfonic acid type hydrophilic monomer (component S5) is added, so that the ionic stability of the obtained resin can be enhanced, and the stability of the paint emulsion is improved in the process of using the resin for a glass fiber film forming agent;

the obtained waterborne polyurethane dispersion resin and the cationic assistant are well compounded, and other solvents are not introduced in the synthesis process, so that the current environmental protection trend is met;

(3) in the preparation process of the aqueous polyurethane-polyurea dispersion resin, the addition of the component S6) is adjusted, so that chain extension can be ensured under the condition of higher carbamido content, and the high-temperature yellowing resistance and mechanical property of the obtained dispersion resin are improved; in the preparation process, by introducing a few amino end-capping ratios (namely adding a small amount of the component S7), the isocyanate end-capped aqueous polyurethane prepolymer can be further subjected to a water chain extension reaction in water under the condition of ensuring high active functional group content, so that the high molecular weight, high urea group content and high active functional group content of the aqueous polyurethane-polyurea dispersion resin are realized, and 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 strength of the resin are further improved, and the preparation method is suitable for wide popularization in the industry of glass fiber film forming agents.

Detailed Description

In order that the technical features and contents 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 by the embodiments set forth herein.

< test methods >

The solid content test method comprises the following steps: taking a proper amount of the aqueous polyurethane-polyurea dispersoid to be detected in a container made of tin foil paper, weighing the weight change before and after 20min of placing at the temperature of 150 ℃, and calculating the solid content of the aqueous polyurethane-polyurea dispersoid.

Particle size test method: measuring the particle size and particle size distribution of a sample to be measured by Dynamic Light Scattering (DLS); in the test, the particle size and the particle size distribution of the aqueous polyurethane-polyurea dispersion are measured by a particle size analyzer of Zetasizer Nano ZS90 of Malvern, the test temperature is 25 ℃, the laser angle is 90 degrees, and the test laser wavelength is 633 nm.

Test method of pH: the test was performed using a pH meter.

Method for measuring viscosity: the measurements were carried out using a BROOKFIELD viscometer, spindle 3/30 rpm.

Method for measuring weight loss on heating (TGA): according to ISO11358 plastic-thermal weight loss method, adopting TGA/DSC3+ of Mettlertriol, the temperature range is 30-600 ℃, and the heating rate is as follows: 10 ℃/min, gas: nitrogen, flow rate: 50 ml/min; the experimental result can obtain a temperature-weight loss rate curve, and the higher the non-decomposition ratio (weight loss rate) at the same temperature, the better the thermal weight loss effect.

Appearance color test method: and (4) observing with naked eyes.

The mechanical property testing method comprises the following steps: according to the GB/T104092 standard, according to the condition of a sample to be tested, a tensile test can be carried out at the tensile speed of 50mm/min and at room temperature, the test result can obtain a stress-strain curve of the sample to be tested, and data such as the tensile strength, the elongation at break, the modulus and the like of the material can be obtained from the curve.

And testing the compounding stability of the cationic auxiliary agent: weighing 20g of the aqueous polyurethane-polyurea dispersion resin emulsion to be tested, adding 1g of 20% cetyl trimethyl ammonium bromide for mixing, stirring for 30min under the condition of 300 r/min for uniformly mixing, and filtering to show that the condition of slag is optimal without generating slag.

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

Solvent resistance test: pouring the waterborne polyurethane-polyurea dispersion resin emulsion to be detected onto a film forming plate, drying for 8 hours at 50 ℃, and then continuously drying for 4 hours at 80 ℃ to obtain a waterborne polyurethane adhesive film; weighing a certain mass (about 1g) of water-based polyurethane adhesive film m1, putting the water-based polyurethane adhesive film m1 into 100ml of acetone, taking out the adhesive film after sealing and soaking for 24h, drying the adhesive film at 80 ℃ for 4h, weighing a ratio of the mass m2 to the mass m2 to the mass m1 of the original adhesive film as a reference (0-100%) of solvent resistance, wherein the higher the ratio is, the better the solvent resistance is.

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

Testing the thermal storage stability: and (3) placing the sample to be detected in a constant-temperature oven at 50 ℃ for one month, and observing whether the appearance of the emulsion is layered or not.

< sources of raw materials >

Component S1):

HDI, (hexamethylene diisocyanate having an NCO content of about 50.0% by weight), available from Vanhua chemical group, Inc.;

IPDI, (isophorone diisocyanate, with an NCO content of about 37.8 wt.%), available from Bayer, Germany;

component S2):

CMA654, (poly (neopentyl glycol adipate-1, 6-hexanediol) diol with a number average molecular weight of 1500 and a functionality of 2) available from dawsonia macrochemistry;

PNA2000, (poly neopentyl glycol adipate diol with number average molecular weight of 2000 and functionality of 2) available from petasites university chemical;

PTMEG2000, (polytetrahydrofuran ether glycol having a number average molecular weight of 2000 and a functionality of 2) available from basf;

component S3):

Ymer^TMn120 (hydroxyl number 112mgKOH/g, number average molecular weight 1200, functionality 2) available from boston;

component S4):

NPG (neopentyl glycol) available from Vanhua chemical group, Inc.;

component S5):

a95 (ethylenediamine ethanesulfonic acid sodium salt), commercially available from ziboen;

component S6):

IPDA (isophoronediamine), available from Bayer, Germany;

hydroxyethylethylenediamine, available from jonan yofta chemical;

component S7):

tris (Tris hydroxymethyl aminomethane) from alatin;

acetone, Vanhua chemical group, Inc.;

BiCat8108 (bismuth based catalyst), which is purchased from the top of the United states.

Cetyl trimethylammonium bromide, available from alatin reagent.

Because of the excess of NCO groups in the system and the high reactivity, the molar ratio of the isocyanate groups to the hydroxyl groups of the polyol (i.e., R value) in the final product is considered to be close to the raw material charge ratio. Therefore, the molar ratio of the isocyanate group and the hydroxyl group of the polyol (i.e., R value) in the following examples and comparative examples was calculated in accordance with the charge ratio of the raw materials of diisocyanate and 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^TMN120, 240g of PNA2000, 16.4g of neopentyl glycol, 0.12g of BiCat8108 and 37g of acetone are stirred and heated to 80 ℃ for reaction for 3 hours until NCO in the system basically reaches or approaches to a theoretical value, and an isocyanate-terminated prepolymer is generated;

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

(3) dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.6g 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 chain extension reaction into a dispersion cup, and adding 433g of water under the high-speed shearing condition of 1500 rpm for shearing and dispersing;

(4) after dispersion, adding a prepared aqueous solution containing Tris (10 g of aqueous solution prepared by adding 40g of water into Tris) into a dispersion cup, and carrying out end-capping reaction for 8-10 minutes to obtain a crude emulsion containing aqueous polyurethane-polyurea;

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky white weak blue-light waterborne polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 346 nm.

Example 2:

HDI、50g IPDI，23g Ymer^TMN120, 240g of PTMEG2000, 16.4g of neopentyl glycol, 0.12g of BiCat8108 and 37g of acetone are stirred and heated to 80 ℃ for reaction for 3 hours until NCO in the system basically reaches or approaches to a theoretical value, and an isocyanate-terminated prepolymer is generated;

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky white weak blue-light waterborne polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 298 nm.

Example 3:

HDI、50g IPDI，23g Ymer^TMN120, 240g of CMA654, 12g of neopentyl glycol, 0.12g of BiCat8108 and 37g of acetone, stirring and heating to 80 ℃ for reaction for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating an isocyanate-terminated prepolymer;

(3) dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.6g 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 chain extension reaction into a dispersion cup, and adding 428g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky white weak blue-light waterborne polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 315 nm.

Example 4:

HDI、50g IPDI，18g Ymer^TMN120, 146g of CMA654, 19.6g of neopentyl glycol, 0.08g of BiCat8108 and 27g of acetone, stirring and heating to 80 ℃ for reaction for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating an isocyanate-terminated prepolymer;

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

(3) dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.2g 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 chain extension reaction into a dispersion cup, and adding 312g of water for shearing dispersion under the high-speed shearing condition of 1500 revolutions per minute;

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky white weak blue-light waterborne polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 328 nm.

Example 5:

HDI、50g IPDI，33g Ymer^TMN120, 225g of CMA654, 12g of neopentyl glycol, 0.2g of BiCat8108 and 52g of acetone, stirred and litersThe temperature is increased to 80 ℃ for reaction for 3h until NCO in the system basically reaches or approaches to a theoretical value, and an isocyanate-terminated prepolymer is generated;

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

(3) dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.6g 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 chain extension reaction into a dispersion cup, and adding 410g of water for shear dispersion under the high-speed shear condition of 1500 revolutions per minute;

(4) after dispersion, adding a prepared aqueous solution containing Tris (11 g of aqueous solution prepared by adding 48g of water to Tris) into a dispersion cup, and carrying out end-capping reaction for 8-10 minutes to obtain a crude emulsion containing aqueous polyurethane-polyurea;

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky white weak blue-light waterborne polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 305 nm.

Example 6:

(4) after the dispersion is finished, adding a water solution containing Tris (which is a water solution prepared by adding 4g of Tris and 16g of water) prepared in advance into a dispersion cup, and carrying out end-capping reaction for 8-10 minutes to obtain a crude emulsion containing aqueous polyurethane-polyurea;

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky white weak blue-light waterborne polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 321 nm.

Example 7:

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

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky weak blue aqueous polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 286 nm.

Comparative example 1:

HDI、50g IPDI，5.3g Ymer^TMN120, 240g of CMA654, 14g of neopentyl glycol, 0.11g of BiCat8108 and 35g of acetone, stirring and heating to 80 ℃ for reaction for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating an isocyanate-terminated prepolymer;

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

(3) dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 9g 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 chain extension reaction into a dispersion cup, and adding 372g of water for shearing dispersion under the high-speed shearing condition of 1500 revolutions per minute;

(5) and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky blue-light waterborne polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 256 nm.

Comparative example 2:

HDI、50gIPDI，23g Ymer^TMN120, 240g of CMA654, 12g of neopentyl glycol, 0.12g of BiCat8108 and 37g of acetone, stirring and heating to 80 ℃ for reaction for 3 hours until NCO in the system basically reaches or approaches a theoretical value, and generating an isocyanate-terminated prepolymer;

(3) dissolving 4g of IPDA, 4g of hydroxyethyl ethylenediamine and 1.6g 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 chain extension reaction into a dispersion cup, adding 420g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing to obtain a crude emulsion containing the waterborne polyurethane-polyurea;

Comparative example 3:

(3) dissolving 4g of IPDA, 2g of hydroxyethyl ethylenediamine and 1.6g 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 chain extension reaction into a dispersion cup, and adding 428g of water under the high-speed shearing condition of 1500 revolutions per minute for shearing and dispersing;

(4) after dispersion, adding a prepared aqueous solution containing Tris (which is an aqueous solution prepared by adding 26g of Tris and 104g of water) into a dispersion cup, and carrying out end-capping reaction for 8-10 minutes to obtain a crude emulsion containing aqueous polyurethane-polyurea;

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky weak blue aqueous polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 281 nm.

Comparative example 4:

HDI、50g IPDI，33g Ymer^TMN120, 400g of CMA654, 0.2g of BiCat8108 and 52g of acetone, stirring and heating to 80 ℃ for reaction for 3 hours until NCO in the system basically reaches or approaches to a theoretical value, and generating an isocyanate-terminated prepolymer;

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

(3) dissolving 3.8g of IPDA, 3.8g of hydroxyethyl ethylenediamine and 2.4g 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 chain extension reaction into a dispersion cup, and adding 620g of water for shearing dispersion under the high-speed shearing condition of 1500 revolutions per minute;

(4) after dispersion, adding a prepared aqueous solution containing Tris (which is an aqueous solution prepared by adding 12g of Tris and 48g of water) into a dispersion cup, and carrying out end-capping reaction for 8-10 minutes to obtain a crude emulsion containing aqueous polyurethane-polyurea;

and (3) desolventizing the crude emulsion in a reduced pressure distillation mode, and removing acetone in the crude emulsion to obtain milky white weak blue aqueous polyurethane-polyurea dispersion resin emulsion, wherein the solid content of the emulsion is 50 wt%, and the particle size of the emulsion is 317 nm.

The performance indexes of the aqueous polyurethane resin prepared in each example and comparative example are shown in tables 1 to 3 below:

TABLE 1 Performance indices of aqueous polyurethane-polyurea dispersion resins

The experimental data in table 1 show that: compared with polyester polyol, due to the fact that the cohesive energy of the polyether polyol is low, ether bonds are easy to rotate and the ether bonds are easy to break at high temperature, the comprehensive performance of the resin prepared by selecting the polyester polyol as the component S2) in the formula system of the aqueous polyurethane-polyurea dispersion resin is superior to that of the resin prepared by selecting the polyether polyol as the component S2).

TABLE 2 Performance indices of aqueous polyurethane-polyurea dispersion resins

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

the waterborne polyurethane-polyurea dispersion resin prepared by the technical scheme of the invention has excellent comprehensive performance; example 3 as a preferred implementation, the obtained resin can achieve better effects on various properties, and the comprehensive properties are improved.

The thermal weight loss of the product can be influenced by reducing the microphase separation degree by adjusting different soft-hard segment proportions (namely, the mixture ratio of the components S1/S2). The test results of examples 3-5 show that the optimum soft-hard segment ratio (the ratio of the components S1/S2) is designed to ensure that the microphase separation degree reaches an optimum state, so that the film forming property is improved, and the aqueous polyurethane-polyurea dispersion resin has high thermal weight loss rate at high temperature under the condition of ensuring the mechanical property.

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

TABLE 3 Performance indices of aqueous polyurethane-polyurea dispersion resins

As can be seen from the experimental data in table 3:

as can be seen from the comparison between example 3 and comparative example 1, the present application, which uses the nonionic hydrophilic group-containing component as the hydrophilic main body and the anionic group-containing component as the co-hydrophilic body, can better improve the compounding stability of the resulting polyurethane-polyurea resin with cations. In contrast, in comparative example 1, the polyurethane resin prepared by using the component containing the anionic group as the 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 assistant, which indicates that the compounded emulsion formed by the main anionic resin and other cationic assistants cannot exist stably when the main anionic resin is used for soaking the glass fiber into the film forming agent; in addition, the high temperature yellowing resistance of the resulting resin is also inferior. The dispersion resin using the nonionic hydrophilic group component as the hydrophilic main body and the anionic group-containing component as the co-hydrophilic body is shown to have better cationic stability and high-temperature yellowing resistance.

As can be seen from comparison of example 3 with 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, particularly in terms of high-temperature yellowing resistance; meanwhile, the mechanical property, the solvent resistance and the thermal weight loss property of the product are all poorer than those of the product obtained in example 3.

As can be seen from comparison between example 3 and comparative example 3, if the amount of component S7) in the system is too large, too high a capping rate will affect the storage stability of the emulsion under high temperature conditions. In comparative example 3, due to the excessively high capping rate, the system is thickened by the hydrophilic action of the excessively introduced hydroxyl groups, resulting in an increase in the initial viscosity of the system, and finally in deterioration of the heat storage stability of the resin.

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

In conclusion, the waterborne polyurethane-polyurea dispersion resin can keep good compounding property with other cationic components in the impregnating compound, and ensures high stability of paint emulsion; meanwhile, the high-strength high-temperature-resistant waterborne polyurethane can obtain high strength and mechanical properties, has excellent high-temperature-resistant yellowing performance and high thermal weight loss retention rate, has solvent resistance superior to that of the traditional waterborne polyurethane, and has a high practical use value.

Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not 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 waterborne polyurethane-polyurea dispersion resin is characterized by being prepared by adopting the following raw materials through reaction:

s1) at least one diisocyanate;

wherein the molar ratio of component S1) to component S2) is 2:1 to 5:1, preferably 2.5:1 to 4: 1;

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

the component S1) is used in an amount of 10 to 45 wt.%, preferably 15 to 25 wt.%;

component S2) is used in an amount of 45 to 75 wt.%, preferably 55 to 70 wt.%;

the component S3) is used in an amount of 3 to 10% by weight, preferably 5 to 8% by weight;

the component S4) is used in an amount of 0 to 10% by weight, preferably 2 to 8% by weight;

the component S5) is used in an amount of 0.1 to 1% by weight, preferably 0.2 to 0.8% by weight;

component S6) is used in an amount of 0.5 to 5 wt.%, preferably 1 to 4 wt.%;

the component S7) is used in an amount of 1 to 5% by weight, preferably 2 to 3% by weight.

3. 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, preferably from one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate; and/or

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 glycol adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 6-hexanediol adipate diol and neopentyl glycol-1, 6-hexanediol adipate diol, preferably from the group consisting of polyethylene glycol adipate-1, 6-hexanediol diol; and/or

The polymerization unit of component S3) contains ethylene oxide, which accounts for 90-100 wt% of the total weight of the non-ionic hydrophilic compound; preferably, the non-ionic hydrophilic compound is selected from polyethylene oxide ether glycols and/or polyethylene glycol methyl ethers, more preferably from polyethylene oxide ether glycols; and/or

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; and/or

Component S5) is selected from one or more of ethylenediamine ethyl sodium sulfonate, 2- (2-aminoethyl) amino propane sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and 1, 2-dihydroxy-3-propane sodium sulfonate, preferably ethylenediamine ethyl sodium sulfonate; and/or

Component S6) is selected from one or more of ethylenediamine, hydroxyethylethylenediamine, hexamethylenediamine, pentamethylenediamine, diethylenetriamine, isophoronediamine and 4, 4-diphenylmethanediamine, preferably from hydroxyethylethylenediamine and/or isophoronediamine.

4. The aqueous polyurethane-polyurea dispersion resin according to claim 1, wherein component S7) is selected from one or more of cyclohexylamine, diethylamine, tris, ethanolamine, diethanolamine and 2-amino-2-methyl-1-propanol, preferably tris.

5. The aqueous polyurethane-polyurea dispersion resin according to any of claims 1 to 4, wherein the starting materials further comprise, based on the total weight of component S1) to component S7):

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

a catalyst, which is added in an amount of 0.01 to 0.05 wt.%, preferably 0.02 to 0.03 wt.%, based on the total weight of component S1) to component S7); the catalyst is preferably selected from dibutyltin dilaurate, cobaltous octoate or BiCat8108, more preferably BiCat 8108.

6. A process for preparing the aqueous polyurethane-polyurea dispersion resin according to any of claims 1 to 5, comprising the steps of:

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

optionally, the low-boiling organic solvent is partially or completely removed by distillation under reduced pressure to obtain the aqueous polyurethane-polyurea dispersion resin.

7. The process according to claim 6, wherein the aqueous polyurethane-polyurea dispersion resin has a solids content of 40 to 60%, preferably 45 to 55%;

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

8. The method according to claim 6, wherein the temperature of the reaction in step (1) is 70 to 80 ℃;

the dissolving and diluting process conditions in the step (2) comprise: the dissolving temperature is 40-50 deg.C, and the dissolving time is 5-10 min;

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

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

9. Use of an aqueous polyurethane-polyurea dispersion resin for the preparation of a glass-fibre-wetting film former, characterized in that the aqueous polyurethane-polyurea dispersion resin is prepared according to any one of claims 1 to 5 or according to any one of claims 6 to 8.

10. The use according to claim 9, wherein in the process of preparing the glass fiber-infiltrated film-forming agent, the aqueous polyurethane-polyurea dispersion resin is compounded with a cationic adjuvant;

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