CN116102993A - RPVB glue, composite carrier prepared from RPVB glue and application of composite carrier - Google Patents

RPVB glue, composite carrier prepared from RPVB glue and application of composite carrier Download PDF

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Publication number
CN116102993A
CN116102993A CN202310034282.6A CN202310034282A CN116102993A CN 116102993 A CN116102993 A CN 116102993A CN 202310034282 A CN202310034282 A CN 202310034282A CN 116102993 A CN116102993 A CN 116102993A
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rpvb
parts
glue
aqueous
polyurethane prepolymer
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黄筱莉
唐丰康
黄敏
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Hangzhou Ruiketai New Material Co ltd
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Hangzhou Ruiketai New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2429/00—Presence of polyvinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The application relates to the technical field of preparation of water-based PVB glue, in particular to RPVB glue, a composite carrier prepared by utilizing the RPVB glue and application of the composite carrier. The RPVB glue is mainly prepared from the following raw materials in parts by weight: 100 parts of aqueous RPVB emulsion, 60-180 parts of aqueous polyurethane prepolymer, 1-5 parts of adhesion promoter, 0.5-2 parts of drier, 2-6 parts of aqueous crosslinking agent and 1-5 parts of pH value regulator; each mole of polyurethane prepolymer in the aqueous polyurethane prepolymer contains 0.04-0.12moL of-NCO; the aqueous RPVB emulsion is mainly prepared from the following raw materials in parts by weight: 100 parts of RPVB powder, 100-120 parts of deionized water, 5-20 parts of nonionic emulsifier, 10-30 parts of cosolvent and 1-3 parts of defoamer. The wear-resistant and hydrolysis-resistant composite material is good in environmental protection, and has good mechanical properties, wear resistance and hydrolysis resistance.

Description

RPVB glue, composite carrier prepared from RPVB glue and application of composite carrier
Technical Field
The application relates to the technical field of preparation of water-based PVB glue, in particular to RPVB glue, a composite carrier prepared by utilizing the RPVB glue and application of the composite carrier.
Background
The polyvinyl butyral PVB resin is prepared from polyvinyl PVA and butyraldehyde, and has excellent transparency, good solubility and good light resistance, water resistance, heat resistance, cold resistance and film forming property. The functional group contained in the modified polyethylene glycol can be subjected to saponification reaction of the phthalide group, and has high adhesive force with materials such as glass, metal (especially aluminum) and the like through various reactions such as acetification and sulfonation of the group. Therefore, the material is widely applied in the fields of manufacturing laminated safety glass, adhesives, ceramic decals, aluminum foil paper, electrical appliance materials, glass fiber reinforced plastic products, fabric treatment agents and the like, and becomes an indispensable synthetic resin material.
Related art application No. 202210000272.6 discloses an aqueous PVB emulsion comprising the following components in parts by weight: 100 parts of PVA, 10-30 parts of water-soluble polyhydroxy compound, 30-50 parts of butyraldehyde, 5-20 parts of water-soluble aldehyde, 10-20 parts of hydrochloric acid, 10-20 parts of liquid alkali, 150-500 parts of deionized water and 0.2-0.5 part of antioxidant. According to the invention, a hydrophilic compound capable of participating in the reaction is directly added into the reaction of PVA solution and butyraldehyde, and after the reaction, residual aldehyde reactant is distilled out, the aqueous RPVB emulsion is directly obtained.
For the related art aqueous PVB emulsion, the applicant finds that the following defects exist in the technical scheme: although aqueous PVB emulsions are environmentally friendly, the aqueous PVB emulsions prepared have the following drawbacks when treated with facestock: the material performance and wear resistance of the water-based PVB emulsion film forming are poorer than those of the solvent-based PVB film forming, so that the application of the water-based PVB emulsion film forming in the field of fabric treatment is limited.
Disclosure of Invention
In order to solve the technical problems, the application provides RPVB glue, a composite carrier prepared by utilizing the RPVB glue and application thereof.
In a first aspect, the application provides an RPVB glue, which is realized by the following technical scheme:
the RPVB glue is mainly prepared from the following raw materials in parts by weight: 100 parts of aqueous RPVB emulsion, 60-180 parts of aqueous polyurethane prepolymer, 1-5 parts of adhesion promoter, 0.5-2 parts of drier, 2-6 parts of aqueous crosslinking agent and 1-5 parts of pH value regulator; the solid content of the aqueous polyurethane prepolymer is 30-50%, and each mole of polyurethane prepolymer in the aqueous polyurethane prepolymer contains 0.04-0.12moL of-NCO; the aqueous RPVB emulsion is mainly prepared from the following raw materials in parts by weight: 100 parts of RPVB powder, 100-120 parts of deionized water, 5-20 parts of nonionic emulsifier, 10-30 parts of cosolvent and 1-3 parts of defoamer.
By adopting the technical scheme, the prepared RPVB glue is good in environmental protection, and has good mechanical property, wear resistance and hydrolysis resistance.
Preferably, the nonionic emulsifier is at least one of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester and fatty amine polyoxyethylene ether; the fatty alcohol-polyoxyethylene ether is at least one of AEO7, MOA-7 and AEO 9; the fatty acid polyoxyethylene ester is at least one of A103, A105 and A110; the fatty amine polyoxyethylene ether is at least one of AC-1200 and AC-1800; the cosolvent consists of acetone and a plasticizer; the mass ratio of the acetone to the plasticizer is (6-8): (1-2); the plasticizer is di-n-hexyl adipate and triethylene glycol-di (2-ethyl-butyrate, and the defoamer is TEGO Di high Foamex 825 defoamer emulsion or Foamex1488 defoamer emulsion.
By adopting the technical scheme, the quality of the prepared RPVB glue can be ensured. In addition, the production and processing difficulty can be reduced, and the quality of the prepared RPVB glue can be ensured. In the application, a certain amount of acetone is adopted as a solvent of the RPVB powder, but the final aqueous RPVB emulsion does not contain the solvent acetone, and the environment friendliness is relatively good.
Preferably, the preparation method of the RPVB powder comprises the following steps:
firstly, recycling waste automobile windshields, cutting off black parts beside products, separating the black glass from transparent glass, selling price of the transparent glass, separating PVB parts simultaneously from black and white, crushing PVB products for the first time, and crushing the PVB products into a net shape so as to facilitate soaking and improving dryness;
immersing the product in the pool, and arranging and stacking the product in order for post-operation, wherein the immersing time is 15-18 days, and the immersing area needs multiple water channels for immersing so as to realize cyclic operation;
step three, crushing for the second time: crushing the product, enabling the dryness of the product to be more than 90%, then flattening, brushing the surface, and improving the cleanliness of the product to be more than 95%;
step four, the product obtained in the step three is divided into strips to be in a noodle shape, so that the cleanliness of the product is further improved, and the dryness of the processed product is more than 98%;
fifthly, placing the product into a cleaning machine to ensure that the product cleanliness is increased to 100%;
step six, granulating, removing water, wherein the water content is lower than 0.01%, and obtaining the RPVB powder.
By adopting the technical scheme, the RPVB powder is recycled, the resource utilization rate is high, the environmental protection performance is good, and the preparation method of the RPVB powder provided by the application is relatively simple and is convenient for industrial production.
Preferably, the aqueous polyurethane prepolymer is prepared from the following raw materials: diisocyanate, polyalcohol, chain extender, bismuth octodecanoate, acetone and deionized water; the molar ratio of the polyol to the chain extender is 1: (2.6-3.2); the chain extender is 1, 4-butanediamine, diethyl toluene diamine and 1, 6-hexanediol; the polyol is high primary hydroxyl modified polyether polyol with the molecular weight of 1000-2000, polycarbonate diol PCDL with the molecular weight of 2000-3000 and modified PTMEG CPOL-MM-200 with the molecular weight of 1950-2050; the molar ratio of the high primary hydroxyl modified polyether polyol with the molecular weight of 1000-2000, the polycarbonate diol PCDL with the molecular weight of 2000-3000 and the modified PTMEG CPOL-MM-200 with the molecular weight of 1950-2050 is (4-6): (3-4): (1-3); the molar amount of-NCO in the diisocyanate is 0.08-0.20mol more than the total molar amount of active functional groups in the polyol and the chain extender.
By adopting the technical scheme, the water-based polyurethane prepolymer and the water-based RPVB emulsion can be compounded for use, so that the overall physical property, weather resistance, wear resistance and environmental protection performance can be improved.
Preferably, the adhesion promoter is TEGO AddBond DS 1300 or TEGO AddBond 1270; the drier is Valirex Aqua Mix 353 or Valirex Aqua Mix 236; the water-based crosslinking agent is at least one of Crosslinker CX-100 matched with Desmodur XP-2802, dispex Ultra FA-4416 and Dispex Ultra FA-4437; the pH regulator is one of VANTEX-T, ceramic AMP-95 and Rhodoline AN-130.
By adopting the technical scheme, the water-based cross-linking agent and the adhesion promoter are compounded, so that the adhesion stability and the mechanical property of the composite substrate can be ensured; the film forming speed can be increased by adding the drier, and the production efficiency of the composite carrier is improved.
Preferably, the preparation method of the RPVB glue comprises the following steps:
step one, preparing an aqueous RPVB emulsion and an aqueous polyurethane prepolymer;
and step two, after uniformly mixing the water-based RPVB emulsion and the water-based polyurethane prepolymer in the step one with accurate metering, sequentially adding the adhesion promoter, the water-based crosslinking agent and the drier with accurate metering, uniformly mixing at 10-25 ℃ and 0.02-0.08MPa, and adding the pH value regulator to adjust the pH value of the system to 6.5-7.2, thus obtaining the finished product RPVB glue.
The preparation method of the RPVB glue is relatively simple, and is convenient for realizing industrialized mass production.
Preferably, the preparation method of the aqueous RPVB emulsion comprises the following steps: dissolving RPVB powder in a cosolvent, adding deionized water, a defoaming agent and a nonionic emulsifier, emulsifying and dispersing at high speed, and distilling under reduced pressure to remove an organic solvent to obtain the finished product of the aqueous RPVB emulsion.
The preparation method of the water-based RPVB emulsion is relatively simple, and is convenient for realizing industrialized mass production.
Preferably, the preparation method of the aqueous polyurethane prepolymer comprises the following steps: firstly weighing polyol, diisocyanate and bismuth octodecanoate according to a formula, uniformly mixing, heating to 85-90 ℃, reacting for 2-3 hours, then adding a chain extender, reacting for 1.5 hours at 70-80 ℃, detecting the NCO content in the system once every 10 minutes, adding acetone to dilute the viscosity when detecting the unreacted NCO content in each mole of diisocyanate to be 0.04-0.12moL, simultaneously cooling to 40-45 ℃, adding triethanolamine to neutralize, finally adding deionized water to uniformly disperse at a high speed, distilling to remove acetone, and dripping deionized water to adjust the solid content to 30-50%, thus obtaining the finished product.
The preparation method of the water-based polyurethane prepolymer is relatively simple, the adopted equipment is relatively low in production cost compared with the existing equipment and the conventional equipment, and the industrial batch production is convenient to realize.
In a second aspect, the present application provides a composite carrier prepared by using RPVB glue, which is implemented by the following technical scheme:
the composite carrier prepared by utilizing the RPVB glue comprises a base material, wherein the RPVB glue is coated on the surface of the base material and is solidified into an RPVB glue layer; the base material is one of release paper and plastic film.
By adopting the technical scheme, the production and processing of the composite carrier are facilitated, the composite carrier is convenient to apply to the field of fabrics, and the composite fabric prepared by adopting the composite carrier has good mechanical property, wear resistance and hydrolysis resistance.
In a third aspect, the application provides a composite carrier prepared by using RPVB glue, which is applied to a fabric, the composite carrier is pressed on the surface layer of the fabric, and the base material is uncovered to compound the RPVB glue layer on the surface layer of the fabric.
By adopting the technical scheme, the composite fabric prepared by adopting the composite carrier has good mechanical property, wear resistance and hydrolysis resistance, and the mechanical property and weather resistance of the base material are effectively improved.
In summary, the present application has the following advantages:
1. the RPVB glue prepared in the application is good in environmental protection performance, has good mechanical properties, wear resistance and hydrolysis resistance, and the composite fabric prepared by the application has good mechanical properties, wear resistance and hydrolysis resistance, so that the mechanical properties and weather resistance of the basic fabric are effectively improved.
2. The preparation method is relatively simple and is convenient for realizing industrialized mass production.
Detailed Description
The present application is described in further detail below in conjunction with comparative examples and examples.
The preparation method of the RPVB powder comprises the following steps:
firstly, recycling waste automobile windshields, cutting off black parts beside the automobile windshields, separating the black glass from transparent glass, and enabling the transparent glass to be sold at a good price, in addition, separating the PVB part from the black glass and the white glass, and carrying out first crushing treatment on the collected PVB product, and crushing the PVB product into a net shape so as to facilitate soaking and improving the dryness;
immersing the product crushed into a net shape in the first step into a pool, wherein the product is orderly arranged and stacked so as to facilitate post-operation, the immersion time is 15 days, the immersion liquid is 5g/L of fatty acid polyoxyethylene ester nonionic surfactant aqueous solution, and the immersion area needs multiple water channels for immersion to realize cyclic operation;
step three, crushing for the second time: crushing the product obtained in the second step for the second time to ensure that the product has the dryness of more than 90%, flattening, brushing impurities on the surface of the product, and improving the cleanliness to more than 95%;
step four, the product obtained in the step three is divided into strips to be in a noodle shape, so that the cleanliness of the product is further improved, and the dryness of the processed product is more than 98%;
fifthly, placing the product into a cleaning machine to ensure that the product cleanliness is increased to 100%;
step six, granulating, removing water, wherein the water content is lower than 0.01%, and obtaining the finished product RPVB powder.
Preparation example
Preparation example 1
The aqueous RPVB emulsion is mainly prepared from the following raw materials in parts by weight: 100 parts of RPVB powder, 120 parts of deionized water, 12 parts of nonionic emulsifier, 24 parts of cosolvent and 1 part of defoamer. The particle size of the RPVB powder is controlled between 200 and 400nm. The defoamer is a Foamex1488 defoamer emulsion. The nonionic emulsifier is fatty alcohol polyoxyethylene ether AEO7. The cosolvent is 18 parts of acetone, 2 parts of di-n-hexyl adipate and 4 parts of triethylene glycol-di (2-ethyl) -butyrate.
The preparation method of the aqueous RPVB emulsion comprises the following steps:
firstly, accurately metering acetone, di-n-hexyl adipate and triethylene glycol-di (2-ethyl) -butyrate, placing the acetone, the di-n-hexyl adipate and the triethylene glycol-di (2-ethyl) -butyrate into a reaction kettle, stirring at 240rpm for 5min, and uniformly mixing to obtain a cosolvent for later use;
and step two, adding RPVB powder into a reaction kettle, dissolving the RPVB powder into the cosolvent prepared in the step one, adding deionized water, foamex1488 defoamer emulsion and fatty alcohol polyoxyethylene ether AEO7, emulsifying and dispersing at a high speed for 30min, distilling under reduced pressure to remove acetone, dripping deionized water, emulsifying and dispersing at a high speed, and obtaining the finished product aqueous RPVB emulsion with the solid content of 43.8%.
Preparation example 2
Preparation 2 differs from preparation 1 in that: the particle size of the RPVB powder is controlled to be 400-800nm.
Preparation example 3
Preparation 3 differs from preparation 1 in that: the particle size of the RPVB powder is controlled between 800 and 2000nm.
Preparation example 4
Preparation example 4 differs from preparation example 1 in that: the particle size of the RPVB powder is controlled to be 4-10 microns.
Preparation example 5
The aqueous polyurethane prepolymer is prepared from the following raw materials:
234.24g of diphenylmethane diisocyanate MDI,
58.68g of isophorone diisocyanate (IPDI),
166.67g of a highly primary hydroxylated modified polyether polyol P-1000 having a molecular weight of 1000,
166.67g of polycarbonate diol PCDL 1012 Polycarbonadiol having a molecular weight of 2000,
55.56g of BASF Pasteur modified PTMEG CPOL-MM-200 having a molecular weight of 2000,
25.47g of 1, 4-butanediamine,
25.75g of diethyltoluenediamine,
34.14g of 1, 6-hexanediol,
0.8g of bismuth octodecanoate,
360g of acetone,
3.8g of triethanolamine,
1800g of deionized water.
The molar ratio of polyol to chain extender is 1:2.6.
the chain extender is 1, 4-butanediamine, diethyl toluene diamine and 1, 6-hexanediol.
The polyol is high primary hydroxyl modified polyether polyol with molecular weight of 1000, polycarbonate diol PCDL with molecular weight of 2000 and modified PTMEG CPOL-MM-200 with molecular weight of 2000, and the molar ratio is 6:3:1. the molar amount of-NCO in the diisocyanate is 0.08 to 0.20mol more than the total molar amount of reactive functional groups in the polyol and the chain extender.
The preparation method of the aqueous polyurethane prepolymer comprises the following steps:
firstly, weighing 166.67g of high primary hydroxyl modified polyether polyol P-1000 with a molecular weight of 1000, 166.67g of polycarbonate diol PCDL 1012 with a molecular weight of 2000, 55.56g of BASF (basic group F) Barnoff modified PTMEG CPOL-MM-200 with a molecular weight of 2000, 234.24g of diphenylmethane diisocyanate MDI, 58.68g of isophorone diisocyanate (IPDI) and 0.8g of bismuth octodecanoate according to a formula, placing the materials in a reaction kettle, stirring and mixing for 10min at room temperature at 200rpm, and uniformly mixing;
step two, heating to 88.5-89.3 ℃ for reaction for 150min, then adding 25.47g of 1, 4-butanediamine, 25.75g of diethyl toluenediamine and 34.14g of 1, 6-hexanediol, adjusting the kettle temperature to 75.8-76.3 ℃ for reaction for 90min, detecting the NCO content in the system once every 10min, diluting the viscosity by adding 360g of acetone when detecting that the unreacted NCO content in each mole of diisocyanate is in the range of 0.12-0.15moL, simultaneously cooling to 40 ℃, adding 3.8g of triethanolamine for neutralization, finally adding 1800g of deionized water for high-speed uniform dispersion,
and step three, distilling to remove acetone, dripping deionized water, uniformly dispersing at a high speed, and adjusting the solid content to 42.0% to obtain the finished product waterborne polyurethane prepolymer.
Preparation example 6
Preparation example 6 differs from preparation example 1 in that: the polyol is high primary hydroxyl modified polyether polyol with molecular weight of 1000, polycarbonate diol PCDL with molecular weight of 2000 and modified PTMEG CPOL-MM-200 with molecular weight of 2000, and the molar ratio is 4:4:3.
preparation example 7
Preparation 7 differs from preparation 1 in that: the polyol is high primary hydroxyl modified polyether polyol with molecular weight of 1000, polycarbonate diol PCDL with molecular weight of 2000 and modified PTMEG CPOL-MM-200 with molecular weight of 2000, and the molar ratio is 45:40:15.
preparation example 8
Preparation 8 differs from preparation 1 in that: the polyol is high primary hydroxyl modified polyether polyol with molecular weight of 1000, polycarbonate diol PCDL with molecular weight of 2000 and modified PTMEG CPOL-MM-200 with molecular weight of 2000, and the molar ratio is 40:40:20.
preparation example 9
Preparation 9 differs from preparation 8 in that: the polyol is high primary hydroxyl modified polyether polyol with a molecular weight of 2000, polycarbonate diol PCDL with a molecular weight of 3000 and modified PTMEG CPOL-MM-200 with a molecular weight of 2000.
Preparation example 10
Preparation 10 differs from preparation 9 in that: the chain extender is 1, 4-butanediamine, perfluoro-2, 5-dimethyl-3, 6-dioxaoctanoic acid and 1, 6-hexanediol. The molar ratio of 1, 4-butanediamine, perfluoro-2, 5-dimethyl-3, 6-dioxaoctanoic acid (CAS No.: 2479-74-5) and 1, 6-hexanediol is 4:1:5.
The aqueous polyurethane prepolymer is prepared from the following raw materials:
234.24g of diphenylmethane diisocyanate MDI,
58.68g of isophorone diisocyanate (IPDI),
222.22g of highly primary hydroxylated modified polyether polyol P-2000 having a molecular weight of 2000,
333.33g of polycarbonate diol PCDL having a molecular weight of 3000 (Yu Kogyo PH 300),
111.11g of BASF Pasteur modified PTMEG CPOL-MM-200 having a molecular weight of 2000,
25.47g of 1, 4-butanediamine,
32.22g of perfluoro-2, 5-dimethyl-3, 6-dioxaoctanoic acid,
42.67g of 1, 6-hexanediol,
1.0g of bismuth octodecanoate,
480g of acetone,
3.8g of triethanolamine,
4.2g of triethanolamine,
2465g of deionized water.
The preparation method of the aqueous polyurethane prepolymer comprises the following steps:
firstly, weighing 222.22g of high primary hydroxyl modified polyether polyol P-2000333.33g of polycarbonate diol PCDL (Ph 300) with a molecular weight of 3000, 111.11g of BASF Pasteur modified PTMEG CPOL-MM-200 with a molecular weight of 2000, 234.24g of diphenylmethane diisocyanate MDI, 58.68g of isophorone diisocyanate (cool IPDI) and 1g of bismuth octodecanoate according to a formula, placing the mixture into a reaction kettle, stirring and mixing the mixture at 240rpm for 12min at room temperature, and uniformly mixing the mixture;
step two, heating to 88.7-89.5 ℃ for reaction for 150min, then adding 25.47g of 1, 4-butanediamine, 32.22g of perfluoro-2, 5-dimethyl-3, 6-dioxaoctanoic acid and 42.67g of 1, 6-hexanediol, adjusting the kettle temperature to 75.5-76.1 ℃ for reaction for 90min, detecting the NCO content in the system once every 10min, adding 480g of acetone for diluting the viscosity when detecting the unreacted NCO content in each mole of diisocyanate to be in the range of 0.12-0.15moL, simultaneously cooling to 40 ℃, adding 4.2g of triethanolamine for neutralization, finally adding 2465g of deionized water for high-speed uniform dispersion,
and step three, distilling to remove acetone, dripping deionized water, uniformly dispersing at a high speed, and adjusting the solid content to be 41.8% to obtain the finished product waterborne polyurethane prepolymer.
PREPARATION EXAMPLE 11
Preparation 11 differs from preparation 1 in that: the chain extender is 1, 4-butanediamine, 1, 6-hexanediol, and the mol ratio of the 1, 4-butanediamine to the 1, 6-hexanediol is 1:1.
Preparation example 12
Preparation 12 differs from preparation 1 in that: the polyol is polycarbonate diol PCDL (Yu Kogyo PH 300)
Preparation example 13
Preparation 13 differs from preparation 1 in that: the polyol is BASF Basoff modified PTMEG CPOL-MM-200 with molecular weight of 2000
PREPARATION EXAMPLE 14
Preparation 14 differs from preparation 1 in that: the polyol is high primary hydroxyl modified polyether polyol P-2000 with molecular weight of 2000.
Examples
Example 1
The RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in preparation example 1, 60 parts of the aqueous polyurethane prepolymer in preparation example 5, 2 parts of a cohesion accelerator TEGO AddBond DS 1300, 0.6 part of a drier Valirex Aqua Mix 353, 3 parts of a Crosslinker CX-100, 1.5 parts of a Dispex Ultra FA-4416 and 2 parts of a pH regulator VANTEX-T.
The preparation method of the RPVB glue comprises the following steps:
step one, preparing an aqueous RPVB emulsion and an aqueous polyurethane prepolymer;
the preparation of the aqueous RPVB emulsion is described in preparation example 1;
preparation of aqueous polyurethane prepolymer see preparation example 5;
and step two, after uniformly mixing the water-based RPVB emulsion and the water-based polyurethane prepolymer in the step one, sequentially adding the adhesion promoter, the water-based crosslinking agent and the drier which are accurately measured, uniformly mixing at 10-15 ℃ and 0.02MPa, adding the pH value regulator, and adjusting the pH value of the system to 6.8-7.2 to obtain the finished product RPVB glue.
A composite carrier prepared by utilizing RPVB glue comprises a base material and an RPVB glue layer composited on the base material. Wherein, the formation mode of RPVB glue film: the prepared RPVB glue is coated on the surface of a substrate and cured to form the RPVB glue. The substrate can be selected from release paper and plastic film. In this embodiment, release paper is preferable.
The composite carrier prepared by the RPVB glue is applied to the fabric, the composite carrier is pressed on the surface layer of the fabric, the base material is uncovered, the RPVB glue layer is compounded on the surface layer of the fabric, and the composite fabric prepared by the composite carrier has good mechanical property, wear resistance and hydrolysis resistance.
Example 2
Example 2 differs from example 1 in that: the RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in preparation example 1, 100 parts of the aqueous polyurethane prepolymer in preparation example 5, 2 parts of a cohesion accelerator TEGO AddBond DS 1300, 0.6 part of a drier Valirex Aqua Mix 353, 3 parts of a Crosslinker CX-100, 1.5 parts of a Dispex Ultra FA-4416, and 2 parts of a pH regulator VANTEX-T.
Example 3
Example 3 differs from example 1 in that: the RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in preparation example 1, 150 parts of the aqueous polyurethane prepolymer in preparation example 5, 2 parts of a cohesion accelerator TEGO AddBond DS 1300, 0.6 part of a drier Valirex Aqua Mix 353, 3 parts of a Crosslinker CX-100, 1.5 parts of a Dispex Ultra FA-4416, and 2 parts of a pH regulator VANTEX-T.
Example 4
Example 4 differs from example 1 in that: the RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in preparation example 1, 180 parts of the aqueous polyurethane prepolymer in preparation example 5, 2 parts of a cohesion accelerator TEGO AddBond DS 1300, 0.6 part of a drier Valirex Aqua Mix 353, 3 parts of a Crosslinker CX-100, 1.5 parts of a Dispex Ultra FA-4416 and 2 parts of a pH regulator VANTEX-T.
Example 5
Example 5 differs from example 1 in that: the aqueous RPVB emulsion in preparation example 1 was replaced with the aqueous RPVB emulsion in preparation example 2.
Example 6
Example 6 differs from example 1 in that: the aqueous RPVB emulsion in preparation example 1 was replaced with the aqueous RPVB emulsion in preparation example 3.
Example 7
Example 7 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 6.
Example 8
Example 8 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 7
Example 9
Example 9 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 8
Example 10
Example 10 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 9.
Example 11
Example 11 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 10.
Example 12
Example 12 differs from example 1 in that: the RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in preparation example 2, 120 parts of the aqueous polyurethane prepolymer in preparation example 10, 2.4 parts of a cohesion accelerator TEGO AddBond DS 1300, 0.8 part of a drier Valirex Aqua Mix 353, 3.6 parts of a Crosslinker CX-100, 1.2 parts of a Dispex Ultra FA-4416 and 1.8 parts of a pH regulator VANTEX-T.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that: the RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in preparation example 1, 30 parts of the aqueous polyurethane prepolymer in preparation example 5, 2 parts of a cohesion accelerator TEGO AddBond DS 1300, 0.6 part of a drier Valirex Aqua Mix 353, 3 parts of a Crosslinker CX-100, 1.5 parts of a Dispex Ultra FA-4416 and 2 parts of a pH regulator VANTEX-T.
Comparative example 2
Comparative example 2 differs from example 1 in that: the RPVB glue is prepared from the following raw materials in parts by weight: 100 parts of the aqueous RPVB emulsion in preparation example 1, 200 parts of the aqueous polyurethane prepolymer in preparation example 5, 2 parts of a cohesion accelerator TEGO AddBond DS 1300, 0.6 part of a drier Valirex Aqua Mix 353, 3 parts of a Crosslinker CX-100, 1.5 parts of a Dispex Ultra FA-4416, and 2 parts of a pH regulator VANTEX-T.
Comparative example 3
Comparative example 3 differs from example 1 in that: the aqueous RPVB emulsion in preparation example 1 was replaced with the aqueous RPVB emulsion in preparation example 4.
Comparative example 4
Comparative example 4 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 11.
Comparative example 5
Comparative example 5 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 12.
Comparative example 6
Comparative example 6 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 13.
Comparative example 7
Comparative example 7 differs from example 1 in that: the aqueous polyurethane prepolymer in preparation example 5 was replaced with the aqueous polyurethane prepolymer in preparation example 14.
Performance test
Detection method/test method
1. Mechanical strength test of resin film: the film to be detected is cured at 130 ℃ according to the test method for detecting the tensile strength and the elongation at break of the GB/T30776-2014_adhesive tape, and the detection equipment is an AGS-X type island body universal tester. The test conditions were: temperature (23+2) °c, relative humidity (50+5)%;
2. weather resistance test: according to the requirements of QB/T4671-2014 'hydrolysis resistance determination of synthetic leather test method', a constant temperature and humidity hydrolysis resistance method is adopted for testing.
3. Peel strength test: the base cloth is a surface layer formed by the RPVB glue prepared in examples 1-12 and comparative examples 1-7, and the peel strength of the surface layer formed by the microfiber paper and the RPVB glue is tested by adopting a method GB/T2791-1995 adhesive T peel strength test method flexible material vs. flexible material.
4. Abrasion resistance test: the wear resistance of the facing layers formed from the RPVB glues prepared in examples 1-12 and comparative examples 1-7 were tested according to the GMW 3208-2012 spin wear test. The degradable coating CS-10 1KG was observed 500 times for breakage. If the CS-10 1KG was not broken 500 times, the CS-10 1KG was carried out 800 times to observe whether the damage was present or not.
Data analysis
Table 1 shows the detection parameters of examples 1 to 12 and comparative examples 1 to 7
Figure SMS_1
As can be seen from the combination of examples 1-12 and comparative examples 1-7 and the combination of table 1, the mechanical properties and peel strength of examples 1-4 are better than those of comparative example 1, and the mechanical properties and peel strength of examples 1-4 are relatively smaller than those of comparative example 2; the weather resistance of the examples 1-4 is better than that of the comparative example 1, and the weather resistance is relatively smaller than that of the comparative example 2, so that the RPVB glue prepared by matching 100 parts of the aqueous RPVB emulsion with 60-180 parts of the aqueous polyurethane prepolymer has better environmental protection performance, and has good mechanical property, wear resistance and hydrolysis resistance.
As can be seen from the combination of examples 1-12 and comparative examples 1-7 and the combination of Table 1, the comparison of examples 1, 5-6 with comparative example 3 shows that the particle size of the RPVB powder is controlled to be 200-2000nm, and the prepared RPVB glue has better environmental protection performance and good mechanical property, wear resistance and hydrolysis resistance. The preferable scheme of mechanical property is that the particle size of RPVB powder is controlled between 200 and 400nm. The preferable economical scheme is that the particle size of the RPVB powder is controlled to be 400-800nm.
As can be seen from the combination of examples 1 to 12 and comparative examples 1 to 7 and the combination of Table 1, examples 1, 7 to 11 and comparative examples 4 to 7 show that an increase in the amount of polycarbonate diol PCDL improves the overall tensile strength but has a negative effect on the tensile breaking rate, and that the use of modified PTMEG CPOL-MM-200 in combination reduces the effect of the decrease in the tensile breaking rate caused by the use of polycarbonate diol PCDL, and that the use of highly primary hydroxylated modified polyether polyol having a molecular weight of 1000 to 2000, polycarbonate diol PCDL having a molecular weight of 2000 to 3000, and modified PTMEG CPOL-MM-200 having a molecular weight of 1950 to 2050 as the polyol ensures good flexibility, tensile strength, and tensile breaking rate of the present application. The molar ratio of the highly primary hydroxylated modified polyether polyol having a molecular weight of 1000 to 2000, the polycarbonate diol PCDL having a molecular weight of 2000 to 3000, and the modified PTMEG CPOL-MM-200 having a molecular weight of 1950 to 2050 is (4 to 6): (3-4): the RPVB glue prepared in the step (1-3) has relatively excellent comprehensive performance.
As can be seen from the combination of examples 1-12 and comparative examples 1-7 and the combination of Table 1, examples 1, 7-11 and comparative examples 4-7 show that the mechanical properties of example 11 are better than those of example 10, but the peel strength of example 11 is reduced, the peel strength of example 11 is still more than 30N/3cm, and the overall antifouling property and abrasion resistance can be improved, and the material is suitable for being used as a surface layer material with antifouling and easy-cleaning requirements.
As can be seen from a comparison of examples 1-12 and comparative examples 1-7 with table 1, example 10 and example 12 show that the overall performance of example 10 is optimal, and that example 12 performs similarly to example 10, but at a relatively low cost, and that example 12 is a preferred embodiment of the present application in view of overall cost and performance.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (10)

1. An RPVB glue, which is characterized in that: the material is mainly prepared from the following raw materials in parts by weight: 100 parts of aqueous RPVB emulsion, 60-180 parts of aqueous polyurethane prepolymer, 1-5 parts of adhesion promoter, 0.5-2 parts of drier, 2-6 parts of aqueous crosslinking agent and 1-5 parts of pH value regulator; the solid content of the aqueous polyurethane prepolymer is 30-50%, and each mole of polyurethane prepolymer in the aqueous polyurethane prepolymer contains 0.04-0.12moL of-NCO; the aqueous RPVB emulsion is mainly prepared from the following raw materials in parts by weight: 100 parts of RPVB powder, 100-120 parts of deionized water, 5-20 parts of nonionic emulsifier, 10-30 parts of cosolvent and 1-3 parts of defoamer.
2. An RPVB glue according to claim 1, characterized in that: the nonionic emulsifier is at least one of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester and fatty amine polyoxyethylene ether; the fatty alcohol-polyoxyethylene ether is at least one of AEO7, MOA-7 and AEO 9; the fatty acid polyoxyethylene ester is at least one of A103, A105 and A110; the fatty amine polyoxyethylene ether is at least one of AC-1200 and AC-1800; the cosolvent consists of acetone and a plasticizer; the mass ratio of the acetone to the plasticizer is (6-8): (1-2); the plasticizer is di-n-hexyl adipate and triethylene glycol-di (2-ethyl-butyrate, and the defoamer is TEGO Di high Foamex 825 defoamer emulsion or Foamex1488 defoamer emulsion.
3. An RPVB glue according to claim 1 or 2, characterized in that: the preparation method of the RPVB powder comprises the following steps:
firstly, recycling waste automobile windshields, cutting off black parts beside products, separating the black glass from transparent glass, selling price of the transparent glass, separating PVB parts simultaneously from black and white, crushing PVB products for the first time, and crushing the PVB products into a net shape so as to facilitate soaking and improving dryness;
immersing the product in the pool, and arranging and stacking the product in order for post-operation, wherein the immersing time is 15-18 days, and the immersing area needs multiple water channels for immersing so as to realize cyclic operation;
step three, crushing for the second time: crushing the product, enabling the dryness of the product to be more than 90%, then flattening, brushing the surface, and improving the cleanliness of the product to be more than 95%;
step four, the product obtained in the step three is divided into strips to be in a noodle shape, so that the cleanliness of the product is further improved, and the dryness of the processed product is more than 98%;
fifthly, placing the product into a cleaning machine to ensure that the product cleanliness is increased to 100%;
step six, granulating, removing water, wherein the water content is lower than 0.01%, and obtaining the RPVB powder.
4. An RPVB glue according to claim 1, characterized in that: the aqueous polyurethane prepolymer is prepared from the following raw materials: diisocyanate, polyalcohol, chain extender, bismuth octodecanoate, acetone and deionized water; the molar ratio of the polyol to the chain extender is 1: (2.6-3.2); the chain extender is 1, 4-butanediamine, diethyl toluene diamine and 1, 6-hexanediol; the polyol is high primary hydroxyl modified polyether polyol with the molecular weight of 1000-2000, polycarbonate diol PCDL with the molecular weight of 2000-3000 and modified PTMEG CPOL-MM-200 with the molecular weight of 1950-2050; the molar ratio of the high primary hydroxyl modified polyether polyol with the molecular weight of 1000-2000, the polycarbonate diol PCDL with the molecular weight of 2000-3000 and the modified PTMEG CPOL-MM-200 with the molecular weight of 1950-2050 is (4-6): (3-4): (1-3); the molar amount of-NCO in the diisocyanate is 0.08-0.20mol more than the total molar amount of active functional groups in the polyol and the chain extender.
5. An RPVB glue according to claim 1, characterized in that: the adhesion promoter is TEGO AddBond DS 1300 or TEGO AddBond 1270; the drier is Valirex Aqua Mix 353 or Valirex Aqua Mix 236; the water-based crosslinking agent is at least one of Crosslinker CX-100 matched with Desmodur XP-2802, dispex Ultra FA-4416 and Dispex Ultra FA-4437; the pH regulator is one of VANTEX-T, ceramic AMP-95 and Rhodoline AN-130.
6. An RPVB glue according to claim 1, characterized in that: the preparation method of the RPVB glue comprises the following steps:
step one, preparing an aqueous RPVB emulsion and an aqueous polyurethane prepolymer;
and step two, after uniformly mixing the water-based RPVB emulsion and the water-based polyurethane prepolymer in the step one, sequentially adding the adhesion promoter, the water-based crosslinking agent and the drier which are accurately measured, uniformly mixing at 10-25 ℃ and 0.02-0.08MPa, adding the pH value regulator, and adjusting the pH value of the system to 6.5-7.2 to obtain the finished product RPVB glue.
7. The RPVB glue of claim 6, wherein: the preparation method of the aqueous RPVB emulsion comprises the following steps: dissolving RPVB powder in a cosolvent, adding deionized water, a defoaming agent and a nonionic emulsifier, emulsifying and dispersing at high speed, and distilling under reduced pressure to remove an organic solvent to obtain the finished aqueous RPVB emulsion.
8. An RPVB glue according to claims 4 and 6, characterized in that: the preparation method of the aqueous polyurethane prepolymer comprises the following steps: firstly weighing polyol, diisocyanate and bismuth octodecanoate according to a formula, uniformly mixing, heating to 85-90 ℃, reacting for 2-3 hours, then adding a chain extender, reacting for 1.5 hours at 70-80 ℃, detecting the NCO content in the system once every 10 minutes, adding acetone to dilute the viscosity when detecting the unreacted NCO content in each mole of diisocyanate to be 0.04-0.12moL, simultaneously cooling to 40-45 ℃, adding triethanolamine to neutralize, finally adding deionized water to uniformly disperse at a high speed, distilling to remove acetone, and dripping deionized water to adjust the solid content to 30-50%, thus obtaining the finished product.
9. A composite carrier prepared by using the RPVB glue of any one of claims 1-8, characterized in that: the RPVB glue is coated on the surface of the base material and is solidified to form an RPVB glue layer; the base material is one of release paper and plastic film.
10. The composite carrier prepared by using the RPVB glue as set forth in claim 9 is applied to a fabric, the composite carrier is pressed on the surface layer of the fabric, the base material is removed by uncovering, and the RPVB glue layer is compounded on the surface layer of the fabric.
CN202310034282.6A 2023-01-10 2023-01-10 RPVB glue, composite carrier prepared from RPVB glue and application of composite carrier Pending CN116102993A (en)

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