CN113527611A - Polyurethane dispersion liquid and preparation method and application thereof - Google Patents
Polyurethane dispersion liquid and preparation method and application thereof Download PDFInfo
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- CN113527611A CN113527611A CN202110861430.2A CN202110861430A CN113527611A CN 113527611 A CN113527611 A CN 113527611A CN 202110861430 A CN202110861430 A CN 202110861430A CN 113527611 A CN113527611 A CN 113527611A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/57—Polyureas; Polyurethanes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/08—Dispersing agents for fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/12—Defoamers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane dispersion liquid and a preparation method and application thereof. A polyurethane dispersion liquid is prepared from the following raw materials in parts by weight: 0.5-10 parts of alkali lignin; 30-60 parts of vegetable oil-based polyol; 10-50 parts of isocyanate; 10-40 parts of a chain extender. Renewable vegetable oil-based polyol and alkali lignin can be used as main film forming substances, so that the problem of shortage of petroleum-based polyol resources can be relieved; in addition, due to the matching of the raw materials, the obtained polyurethane dispersion can be a water-based dispersion, and after the polyurethane dispersion is prepared into a polyurethane film or polyurethane leather-filled paper, the mechanical properties of the corresponding film and the corresponding leather-filled paper can be improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyurethane dispersion liquid, and a preparation method and application thereof.
Background
Polyurethane (PU) is a copolymer having a microphase crystal structure in which a molecular chain is composed of soft segments and hard segments by reacting diisocyanate with polyol, and is mainly classified into foams, adhesives, elastomers, films, etc., and is widely used in the fields of biomedicine, construction, automobiles, aerospace, etc. because of its excellent mechanical properties and abrasion resistance. In recent years, polyurethanes have been developed extensively worldwide and are one of the six most widely used synthetic polymers in the world. An investigation of make internal disorder or usurp showed that the global polyurethane mass reached 2120 kilotons in 2016, while it was estimated that the polyurethane production would continue to maintain a 3% annual average growth rate.
Conventional polyurethanes are usually prepared from toxic isocyanates and petroleum-based polyols as raw materials by using organic solvents as dispersions, and a large amount of toxic substances and Volatile Organic Compounds (VOCs) are generated during preparation and use. The waterborne polyurethane is a polymer system which uses water to replace an organic solvent, and the water is used as a dispersion medium, so that the waterborne polyurethane has the advantages of low pollution degree, safety, reliability, good compatibility and the like, and is widely used for coatings, adhesives, elastomers, printing ink and soft and hard foams.
However, with the development of resources, the resources of petroleum-based polyols are more and more tense, and meanwhile, the existing waterborne polyurethane still has the problems of difficult degradation, poor mechanical properties and the like.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a polyurethane dispersion liquid which can take renewable vegetable oil-based polyol and alkali lignin as main film forming substances, thereby relieving the problem of shortage of petroleum-based polyol resources; in addition, due to the matching of the raw materials, the obtained polyurethane dispersion can be a water-based dispersion, and after the polyurethane dispersion is prepared into a polyurethane film or polyurethane leather-filled paper, the mechanical properties and the degradation properties of the corresponding film and leather-filled paper can be improved.
The invention also provides a preparation method of the polyurethane dispersion liquid.
The invention also provides leather-filled paper prepared from the raw materials comprising the polyurethane dispersion liquid.
The invention also provides a preparation method of the leather-filled paper.
According to one aspect of the invention, a polyurethane dispersion is provided, and the preparation raw materials comprise the following components in parts by weight:
0.5-10 parts of alkali lignin;
30-60 parts of vegetable oil-based polyol;
10-50 parts of isocyanate;
10-40 parts of a chain extender.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
the vegetable oil is triglyceride generated by saturated or unsaturated fatty acid and glycerol, is derived from plants, has green, sustainable, cheap and renewable properties, and can be used for preparing new products with various chemical transformation possibilities;
the alkali lignin is used as a byproduct of pulping and papermaking, is a second most natural organic carbon macromolecular compound on the earth, has wide sources and rich product, and has active groups such as aromatic group, phenolic hydroxyl group, alcoholic hydroxyl group, carbon-based conjugated double bond and the like in the molecular structure, so that the alkali lignin can be subjected to a plurality of chemical reactions such as oxidation, reduction, hydrolysis, alcoholysis, acid hydrolysis methoxy group, carboxyl group, photolysis, phthalylation, sulfonation, alkylation, halogenation, nitration, polycondensation, graft copolymerization and the like;
therefore, the pressure of shortage of petroleum resources can be alleviated by using renewable resources such as alkali lignin derived from plants and vegetable oil-based polyols as the main film-forming substance of the polyurethane dispersion liquid; in addition, because the alkali lignin contains abundant active groups, the water resistance, solvent resistance and mechanical properties of the polyurethane dispersion film-forming material can be improved after the alkali lignin is used for preparing the polyurethane dispersion liquid, so that the application range and application value of the alkali lignin are widened; most importantly, as the plant source raw materials are used as film forming substances of the polyurethane dispersion liquid, the degradation performance of the polyurethane after film forming is greatly improved, the environmental pressure is relieved, and an effective and feasible solution is provided for the problems of environmental pollution and the like.
In some embodiments of the invention, the polyurethane dispersion has a solids content of 20 to 50%.
In some preferred embodiments of the present invention, the polyurethane dispersion has a solids content of about 30%.
In some embodiments of the invention, the polyurethane dispersion is an aqueous polyurethane dispersion.
In some embodiments of the present invention, the raw material for preparing the polyurethane dispersion comprises 4 to 8 parts by weight of alkali lignin.
In some embodiments of the invention, the method for producing alkali lignin comprises the steps of:
A1. adjusting the crude alkali lignin aqueous solution to be alkaline, and removing precipitated impurities;
A2. acid precipitation is carried out on the liquid phase mixture obtained in the step A1;
A3. washing the precipitate obtained in the step A2.
In some embodiments of the invention, in step a1, the crude alkali lignin in the aqueous crude alkali lignin solution is selected from industrial alkali lignin.
In some embodiments of the invention, the industrial alkali lignin is purchased from sunshine wallace paper industry, ltd.
In some embodiments of the invention, in step a1, the crude alkali lignin in the aqueous crude alkali lignin solution has a mass percentage of 20-50%.
In some embodiments of the invention, in step a1, the aqueous crude alkali lignin solution has a crude alkali lignin content of about 30% by weight.
In some embodiments of the present invention, in step a1, the alkaline regulator is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In some embodiments of the present invention, in step a1, the alkaline regulator is a 5-10% by mass aqueous solution of sodium hydroxide.
In some embodiments of the invention, in step A1, the basic pH is 12-14.
In some embodiments of the present invention, step a1 further comprises stirring for homogenization between the adjusting to alkalinity and the removing of precipitated impurities.
In some embodiments of the invention, the temperature for stirring homogenization is 60-70 ℃.
In some embodiments of the invention, the stirring homogenization is temperature-controlled under water bath conditions.
In some embodiments of the invention, the stirring and homogenizing time is 10-30 min.
In some embodiments of the invention, the stirring is for about 15 min. In some embodiments of the present invention, in step a2, the acid is precipitated by using at least one of hydrochloric acid, sulfuric acid, hydrobromic acid and nitric acid.
In some embodiments of the present invention, in step a2, the acid is precipitated by using hydrochloric acid with a mass percent of 10-20%.
In some embodiments of the present invention, in step a2, the acid is precipitated using hydrochloric acid having a mass percent of about 12%.
In some embodiments of the present invention, in the step A2, the pH of the acid precipitate is 2-3.
In some embodiments of the invention, the temperature of the acid precipitation in step a2 is 60-70 ℃.
In some embodiments of the invention, in step a3, the end point of the wash is: the waste water produced by washing is near neutral.
In some embodiments of the invention, step a3 further comprises drying and grinding after the washing.
In some embodiments of the invention, the temperature of the drying after washing in step a3 is 60-80 ℃.
In some embodiments of the invention, in step a3, the drying after washing is at least one of vacuum drying and hot air drying.
In some embodiments of the invention, in step a3, the method of milling after washing is ball milling.
In some embodiments of the present invention, the polyurethane dispersion is prepared from 40 to 50 parts by weight of a vegetable oil-based polyol.
In some embodiments of the invention, the vegetable oil-based polyol has an average molecular weight of 1000-4000.
In some preferred embodiments of the present invention, the vegetable oil-based polyol has an average molecular weight of about 2000.
In some embodiments of the present invention, the process for preparing the vegetable oil based polyol comprises the steps of:
B1. carrying out epoxidation reaction on vegetable oil under the action of a first acid catalyst and an oxidant;
B2. carrying out ring opening reaction on the product obtained in the step B1 under the action of a second acid catalyst and a ring opening agent to obtain the catalyst;
in some embodiments of the invention, in step B1, the vegetable oil is selected from at least one of sunflower oil, rapeseed oil, castor oil, linseed oil, palm oil, soybean oil, peanut oil and biorefinery glycerol.
In some embodiments of the invention, in step B1, the first acid catalyst is selected from at least one of acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid.
In some preferred embodiments of the present invention, in step B1, the first acid catalyst is selected from sulfuric acid.
In some embodiments of the invention, in step B1, the oxidizing agent is selected from hydrogen peroxide.
In some preferred embodiments of the present invention, in step B1, the oxidizing agent is hydrogen peroxide with a mass concentration of 30% to 80%.
In some preferred embodiments of the present invention, in step B1, the oxidizing agent is hydrogen peroxide with a mass concentration of about 50%.
The oxidizing agent is measured by mass of an aqueous solution of the oxidizing agent.
In some embodiments of the invention, in step B1, the mass ratio of the vegetable oil, the first acid catalyst and the oxidizing agent is 100: (1-5): (30-70).
In some embodiments of the invention, the temperature of the epoxidation reaction in step B1 is in the range of 40 to 80 ℃.
In some embodiments of the present invention, in step B1, the epoxidation reaction time is from 5 to 10 hours.
In some embodiments of the present invention, in step B1, the epoxidation reaction time is 6 to 8 hours.
In some embodiments of the invention, in step B2, the second acid catalyst is selected from at least one of acetic acid, hydrochloric acid, sulfuric acid, and phosphoric acid.
In some embodiments of the invention, the first acid catalyst and the second acid catalyst may be the same or different.
In some embodiments of the invention, in step B2, the ring opener comprises at least one of an alcohol and an alcohol amine.
In some embodiments of the invention, in step B2, the ring opener comprises at least one of methanol, ethanol, and isopropanol.
In some preferred embodiments of the present invention, in step B2, the ring opener is selected from methanol.
The ring-opening agent can react with the product obtained in the step B1 to improve the quality of the obtained vegetable oil-based polyol, and simultaneously, the generation of side reactions is reduced, so that the utilization rate of raw materials is improved.
In some embodiments of the invention, in step B2, the mass ratio of the product from step B1, the second acid catalyst, and the ring-opener is 100: (1-5): (10-50).
In some embodiments of the invention, the temperature of the ring-opening reaction in step B2 is 80-150 ℃.
In some embodiments of the invention, the temperature of the ring-opening reaction in step B2 is about 90 ℃.
In some embodiments of the invention, in step B2, the ring-opening reaction time is 2 to 6 hours.
In some embodiments of the invention, in step B2, the ambient pressure of the ring-opening reaction is 0.1 to 0.5 MPa.
In some embodiments of the invention, in step B2, the ambient pressure of the ring-opening reaction is about 0.3 MPa.
In some embodiments of the present invention, the raw material for preparing the polyurethane dispersion comprises 20 to 30 parts by weight of the isocyanate.
In some embodiments of the present invention, the isocyanate is selected from diisocyanates.
In some embodiments of the invention, the diisocyanate is selected from 1, 5-pentamethylene diisocyanate.
In some embodiments of the invention, the 1, 5-pentamethylene diisocyanate is available from mitsui chemistry.
In some embodiments of the invention, the 1, 5-pentamethylene diisocyanate is a biobased product, wherein 70 wt% is derived from plants, that is, the biobased content of the 1, 5-pentamethylene diisocyanate is 70 wt%.
The isocyanate adopted by the invention also has higher plant-based content, so that the plant-based content in the obtained polyurethane dispersion liquid is further improved, and the degradability of a product prepared from the polyurethane dispersion liquid is further improved. In some embodiments of the invention, the molar ratio of isocyanate to vegetable oil based polyol is (1.5-4): 1.
in some preferred embodiments of the present invention, the molar ratio of isocyanate to vegetable oil based polyol is (1.5-3): 1.
in some embodiments of the invention, the molar ratio is the molar ratio of the isocyanate and the vegetable oil based polyol functional groups (NCO/OH).
In some embodiments of the invention, the chain extender comprises a first chain extender and a second chain extender.
In some embodiments of the present invention, the first chain extender is added in an amount of 5 to 20 parts by weight.
In some preferred embodiments of the present invention, the first chain extender is added in an amount of 5 to 15 parts by weight.
In some embodiments of the invention, the first chain extender is selected from at least one of 1, 4-Butanediol (BDO), diethylene glycol (DEG), 1, 6-hexanediol, glycerol, triethylene glycol, sorbitol, Diethylaminoethanol (DEAE).
In some preferred embodiments of the present invention, the first chain extender is selected from 1, 4-Butanediol (BDO).
In some embodiments of the present invention, the mass ratio of the added amount of the alkali lignin to the added amount of the first chain extender is 1: (1-19).
In some embodiments of the present invention, the alkali lignin is added in an amount of 5 to 30% by weight of the first chain extender.
In some embodiments of the present invention, the second chain extender is added in an amount of 5 to 20 parts by weight.
In some preferred embodiments of the present invention, the second chain extender is added in an amount of 5 to 15 parts by weight.
In some embodiments of the invention, the second chain extender is an anionic chain extender.
In some embodiments of the invention, the second chain extender is selected from at least one of 2, 2-dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), sodium 1, 2-propanediol-3-sulfonate and sodium 1, 4-butanediol-2-sulfonate.
In some embodiments of the invention, the second chain extender is selected from 2, 2-dimethylolpropionic acid (DMPA).
In some embodiments of the present invention, the raw materials for preparing the polyurethane dispersion further include at least one of a neutralizer, a catalyst, a solvent, and water.
In some embodiments of the present invention, the neutralizing agent is added in an amount of 5 to 20 parts by weight.
In some preferred embodiments of the present invention, the neutralizing agent is added in an amount of 5 to 15 parts by weight.
In some preferred embodiments of the present invention, the neutralizing agent is at least one selected from the group consisting of triethylamine, ammonia water, and sodium hydroxide, in parts by weight.
In some preferred embodiments of the present invention, the neutralizing agent is selected from triethylamine, based on parts by weight.
In some embodiments of the invention, the catalyst is selected from at least one of dibutyltin dilaurate and stannous octoate.
In some embodiments of the invention, the catalyst is selected from dibutyltin dilaurate.
In some embodiments of the present invention, the solvent is added in an amount of 10 to 50 parts by weight.
In some preferred embodiments of the present invention, the solvent is added in an amount of 20 to 40 parts by weight.
In some preferred embodiments of the present invention, the solvent is added in an amount of 2 to 10ml by volume.
In some preferred embodiments of the present invention, the solvent is added in an amount of about 5ml by volume.
In some embodiments of the invention, the solvent is selected from at least one of N, -Dimethylformamide (DMF), N-methylpyrrolidone (NMP), acetone, and Methyl Ethyl Ketone (MEK).
In some preferred embodiments of the present invention, the solvent is selected from acetone.
In some embodiments of the invention, the water is added in an amount of 100-500 parts.
According to a further aspect of the present invention, there is provided a method for preparing the polyurethane dispersion, comprising the steps of:
s1, carrying out prepolymerization reaction on the alkali lignin, the vegetable oil-based polyol, a first chain extender and isocyanate;
and S2, adding a second chain extender into the mixture obtained in the step S1, and neutralizing and emulsifying to obtain the polyurethane foam material.
The preparation method according to a preferred embodiment of the present invention has at least the following advantageous effects:
the preparation method provided by the invention has reasonable charging sequence and reasonable raw material proportion, so that the polyurethane dispersion liquid has excellent dispersion performance and other parameters.
In some embodiments of the present invention, in step S1, the prepolymerization reaction is performed under the action of the catalyst.
In some embodiments of the invention, the mass of the catalyst added is 0.02-0.2% of the mass of the film-forming material in the reaction mixture obtained in step S1.
The mass of the film forming substance is the sum of the masses of the alkali lignin, the vegetable oil-based polyol, the isocyanate and the chain extender.
In some preferred embodiments of the present invention, the added mass of the catalyst is 0.1% of the total mass of the mixture obtained in step S1.
In some embodiments of the present invention, in step S1, before the isocyanate and the catalyst are added, the reaction system is subjected to an air-isolated treatment with an isolation gas.
In some embodiments of the present invention, in step S1, the temperature of the prepolymerization reaction is 60-80 ℃.
In some embodiments of the present invention, in step S1, the temperature of the prepolymerization reaction is 70-80 ℃.
In some embodiments of the present invention, in step S1, the temperature of the prepolymerization reaction is accomplished by means of an oil bath.
In some embodiments of the present invention, in step S1, the prepolymerization time is 2-6 h.
In some embodiments of the present invention, in step S1, the prepolymerization time is 4-6 h.
In some embodiments of the present invention, in step S1, the prepolymerization reaction is performed under stirring.
In some embodiments of the present invention, the stirring speed for the prepolymerization reaction is 120-300 rpm.
In some embodiments of the present invention, the stirring speed for the prepolymerization reaction is 200-300 rpm.
In some embodiments of the present invention, in step S1, when the residual molar amount of isocyanate in the mixture after the prepolymerization reaction is 10-20% of the molar amount at the beginning of the reaction, isocyanate in an amount of 80-90% of the material is reacted.
In some embodiments of the present invention, the reaction temperature after the addition of the second chain extender is 40 to 80 ℃ in step S2.
In some embodiments of the present invention, the reaction temperature after the addition of the second chain extender in step S2 is about 70 ℃.
In some embodiments of the present invention, the reaction time after the addition of the second chain extender in step S2 is 2 to 6 hours.
In some embodiments of the present invention, the reaction time after the addition of the second chain extender in step S2 is about 2 hours.
In some embodiments of the present invention, in step S2, the reaction after the addition of the second chain extender is performed under stirring, and the stirring speed is 120-300 rpm.
In some embodiments of the present invention, in step S2, the reaction after the addition of the second chain extender is performed under stirring, and the stirring speed is about 250 rpm.
In some embodiments of the present invention, in step S2, the reaction after the addition of the second chain extender is stopped when the amount of the substance of the remaining isocyanate is 5 to 15% of the molar amount of the isocyanate at the beginning of the reaction.
The first function of the second chain extender is to carry out chain extension on polyurethane, and the second function is to improve the hydrophilicity of the obtained polyurethane so as to form uniformly dispersed polyurethane dispersion liquid.
In some embodiments of the present invention, the solvent may be further included in step S2, added simultaneously with the second chain extender; the solvent and the second chain extender also function to adjust the viscosity of the reaction system obtained in step S2.
In some embodiments of the present invention, in step S2, the temperature of neutralization is 0-50 ℃.
In some preferred embodiments of the present invention, the temperature of the neutralization is about 50 ℃ in step S2.
In some embodiments of the invention, in step S2, the neutralization time is 0.5-2 h.
In some embodiments of the invention, the neutralization time in step S2 is about 50 min.
In some embodiments of the present invention, in step S2, the water is added during the emulsification.
In some embodiments of the present invention, in step S2, the emulsifying time is 1-4 h.
In some embodiments of the present invention, the emulsification time in step S2 is about 2 hours.
In some embodiments of the invention, the emulsification is achieved by stirring.
In some embodiments of the present invention, the rotation speed of the stirring in the emulsification is 2000-8000 rpm.
In some embodiments of the invention, the agitation is at about 3000rpm during the emulsification.
In some embodiments of the present invention, in step S2, in order to further adjust the solid content of the polyurethane dispersion, a part of the solvent may be removed by rotary evaporation after the emulsification.
In some embodiments of the invention, the temperature of the rotary evaporation is 30-60 ℃.
In some embodiments of the invention, the temperature of the rotary evaporation is about 40 ℃.
In some embodiments of the present invention, steps S1 to S2 are performed under the condition of isolating gas from air.
In some embodiments of the present invention, the barrier gas is at least one of nitrogen and an inert gas unless otherwise specified.
In some embodiments of the present invention, the preparation method of the polyurethane dispersion is performed in a four-neck flask, and the reflux condenser, the isolated gas inlet, the stirrer and the temperature control system are respectively connected.
According to a further aspect of the present invention, there is provided a leathered paper, the raw material for preparing the leathered paper comprises a leathered paper pulp, and the raw material for preparing the leathered paper pulp comprises the polyurethane dispersion.
The leatherette paper according to a preferred embodiment of the invention has at least the following beneficial effects:
at present, the polyurethane leather-filled paper on the market is prepared from raw materials which usually comprise petroleum-based polyurethane dispersion liquid, so that the obtained polyurethane leather-filled paper has no degradability, and simultaneously, the raw materials of the polyurethane dispersion liquid are non-renewable materials, so that the polyurethane leather-filled paper is not environment-friendly in the true sense, and the application field has certain limitation.
The leather-filled paper prepared by the invention has the advantages that the raw materials for preparation comprise the polyurethane dispersion liquid, the main raw materials are from plants, the sources are rich, the obtained leather-filled paper is degradable, environment-friendly and nontoxic, the problems of toxicity, pungent smell and the like of the traditional leather-filled paper are solved, and the leather-filled paper is environment-friendly in the true sense.
The leatherette paper provided by the invention is saturated and bright in color, not easy to fade, has genuine leather texture and excellent physical properties, has the advantages of wear resistance, tear resistance, water resistance, solvent resistance and the like, can be repeatedly utilized, solves the problem of short boards with limited application and the like, and has very wide market application prospect and wide application field.
In some embodiments of the present invention, the raw material for preparing the leathered paper slurry further comprises at least one of a thickener, a defoamer and a leveling agent.
In some embodiments of the invention, the leathered paper pulp comprises 0.1% to 1% of a thickener, in mass percent.
In some embodiments of the invention, the leathered paper pulp contains 0.3% of a thickener, in mass percent.
In some embodiments of the invention, the kraft pulp includes 0.1% to 1% by mass of a defoamer.
In some embodiments of the invention, the kraft pulp includes 0.2% by mass of a defoamer.
In some embodiments of the invention, the leather-filled paper pulp contains 0.1-1% of leveling agent by mass percentage.
In some embodiments of the invention, the leather-filled paper pulp contains 0.1% of leveling agent by mass percentage.
In some embodiments of the invention, the balance of the leatherette paper pulp is the polyurethane dispersion, in mass percent.
In some embodiments of the invention, the leatherette paper may be used in luxury gift boxes, jewel boxes, cosmetic boxes, photo albums, books, and the like.
According to another aspect of the invention, the preparation method of the leather-covered paper is provided, and comprises the steps of coating the leather-covered paper pulp on the surface of a paper substrate, and sequentially carrying out drying, matte treatment and surface post-treatment.
In some embodiments of the present invention, in the method for preparing the leathered paper, the leathered paper slurry is prepared by mixing the polyurethane dispersion, the thickener, the defoamer, and the leveling agent, then performing centrifugal defoaming, and then standing.
In some embodiments of the present invention, the centrifugal rotational speed of the centrifugal defoaming is 3000-8000 rpm.
In some preferred embodiments of the present invention, the rotational speed of the centrifugal debubbling is about 3000 rpm.
In some embodiments of the invention, the centrifugation time for the centrifugal debubbling is 10 to 30 min.
In some preferred embodiments of the present invention, the centrifugation time for the centrifugal debubbling is about 15 min.
In some embodiments of the invention, the time of standing is 5-30 min.
In some embodiments of the invention, in the method of making the leathered paper, the coating has a thickness of 0.1 to 1 mm.
In some preferred embodiments of the present invention, in the method for preparing the leathered paper, the coating has a thickness of 0.5 to 1 mm.
In some embodiments of the present invention, in the method for preparing the leathered paper, the method for coating is selected from one of blade coating, roll coating and air knife coating.
In some embodiments of the invention, the method of coating is selected from knife coating.
In some embodiments of the present invention, in the method for preparing the leathered paper, the drying method is any one of hot air drying, drying cylinder drying and infrared drying.
In some preferred embodiments of the present invention, in the method for preparing the leathered paper, the drying method is hot air drying.
In some embodiments of the present invention, in the method for preparing the leathered paper, the drying temperature is 60 to 120 ℃.
In some embodiments of the present invention, in the method for preparing the leathered paper, the drying temperature is 60 to 100 ℃.
In some embodiments of the present invention, in the method of preparing the leathered paper, the method of surface post-treatment is at least one of embossing and calendering.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 shows an infrared test spectrum of a polyurethane dispersion obtained in example 1 of the present invention and a film formed of an isocyanate used therein.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated. In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The embodiment prepares a polyurethane dispersion liquid, and the specific process is as follows:
D1. preparing alkali lignin:
d1a, dissolving industrial alkali lignin purchased from sunshine China paper industry Co., Ltd as a raw material in deionized water to prepare a solution with the mass concentration of 30%;
d1b, adjusting the pH value of the solution obtained in the step D1a to 12 by using sodium hydroxide with the mass concentration of 10.0%, stirring the obtained mixed system in a water bath at 70 ℃ for 15min, and filtering to remove insoluble impurities;
d1c, performing acid precipitation on the filtrate obtained in the step D1b at 70 ℃ by using a hydrochloric acid solution with the mass concentration of 12%, specifically, adjusting the pH of the filtrate obtained in the step D1b to 2, and filtering;
d1d, washing the filter residue used in the step D1c with deionized water in an inverse mode until the pH value of the filtrate is neutral, then putting the filter residue into a 60 ℃ oven for vacuum drying, and performing ball milling to obtain alkali lignin;
D2. preparation of vegetable oil-based polyol:
d2a, performing epoxidation reaction on linseed oil serving as a raw material for 6 hours in an environment of a sulfuric acid catalyst and hydrogen peroxide (the mass concentration is about 50.0%), wherein the mass ratio of the raw materials is as follows: hydrogen peroxide: sulfuric acid catalyst 100: 60: 2, controlling the reaction temperature at 60 ℃;
d2b, carrying out pressure ring-opening reaction on the epoxidized vegetable oil obtained in the step D2a for 4 hours under the action of a sulfuric acid catalyst and methanol, wherein the mass ratio of the raw materials is that the epoxidized vegetable oil: methanol: acid catalyst 100: 40: 2, the reaction temperature is 90 ℃, and the pressure is 0.3 MPa;
D3. preparation of polyurethane dispersion:
d3a, adopting a prepolymerization method, uniformly mixing 0.5 part of refined alkali lignin dissolved in 10% acetone in mass fraction of a reaction film-forming substance, 50 parts of bio-based polyol and 9.5 parts of BDO (first chain extender) according to a certain mass fraction ratio, stirring at the speed of 250rpm, adding 30 parts of PDI (Poly lactic acid) and 0.1% dibutyltin dilaurate (catalyst) in mass fraction of the film-forming substance (namely 0.1g), and adding N2Heating and reacting for 5 hours at 70 ℃ in the atmosphere, and stopping when the amount of NCO substance is 10% +/-0.011% of the addition amount;
d3b, adding 10 parts by weight of DMPA (second chain extender) and 5ml of acetone into the mixture obtained in the step D3a to reduce the viscosity, controlling the stirring speed at 250rpm, heating and reacting at 70 ℃ for 2 hours, and stopping when the amount of NCO substance is 5% +/-0.0055% of the addition amount;
and D3c, cooling the mixture obtained in the step D3b to 50 ℃, adding 10 parts by weight of TEA (neutralizing agent) for neutralization reaction for 50min, then adding 200 parts by weight of deionized water, emulsifying and dispersing at 3000rpm for 2h, and finally removing the solvent acetone by rotary evaporation at 40 ℃ to obtain a polyurethane dispersion liquid with the solid content of 30%, wherein the plant-based content reaches 71.5%.
Plant-based content ═ m(PDI)×70％+m(alkali lignin)+m(vegetable-based polyol))/(m(PDI)+m(alkali lignin)+m(vegetable-based polyol)+m(BDO)+m(DMPA))×100％；
Of which 70% is the bio-based content of PDI.
In other embodiments, methods for calculating plant-based content are described herein.
The equation for this example is as follows, where DBTDL represents dibutyltin dilaurate:
example 2
This example prepares a polyurethane dispersion, which differs from example 1 in the following specific procedure:
(1) in the step D3a, the addition amount of the alkali lignin is 1 part by weight, and the addition amount of the BDO is 9 parts by weight;
(2) in step D3c, the resulting polyurethane dispersion had a plant-based content of about 72%.
Example 3
This example prepares a polyurethane dispersion, which differs from example 1 in the following specific procedure:
(1) in the step D3a, the addition amount of the alkali lignin is 1.5 parts by weight, and the addition amount of the BDO is 8.5 parts by weight;
(2) in step D3c, the resulting polyurethane dispersion had a plant-based content of about 72.5%.
Example 4
This example prepares a polyurethane dispersion, which differs from example 1 in the following specific procedure:
(1) in the step D3a, the addition amount of the alkali lignin is 2 parts by weight, and the addition amount of the BDO is 8 parts by weight;
(2) in step D3c, the resulting polyurethane dispersion had a plant-based content of approximately 73%.
Example 5
This example prepares a polyurethane dispersion, which differs from example 1 in the following specific procedure:
(1) in the step D3a, the addition amount of the alkali lignin is 2.5 parts by weight, and the addition amount of the BDO is 7.5 parts by weight;
(2) in step D3c, the resulting polyurethane dispersion had a plant-based content of approximately 73.5%.
Example 6
This example prepares a polyurethane dispersion, which differs from example 1 in the following specific procedure:
(1) in the step D3a, the addition amount of the alkali lignin is 3 parts by weight and accounts for 30% of the mass of the BDO;
(2) in step D3c, the resulting polyurethane dispersion had a plant-based content of about 74%.
Example 7
The embodiment prepares the leather-filled paper, and the specific steps are as follows:
E1. preparing leather-covered paper pulp: the raw materials comprise 200 parts of the polyurethane dispersion liquid obtained in the example 1, 0.3 percent of thickening agent (Dow chemical, EPP112), 0.2 percent of defoaming agent (CK-337, Technology Co., Ltd.) and 0.1 percent of flatting agent (OFX-0400 silicone oil, Taojin chemical Co., Ltd.) by mass, the raw materials are uniformly stirred, and are subjected to high-speed centrifugal defoaming at 3000rpm for 15min and standing for 30min to obtain the paper pulp;
E2. and E1, coating the leather-covered paper pulp on the surface of a paper base in a coating thickness of 0.5mm, drying by hot air at 80 ℃, calendaring and embossing to obtain the leather-covered paper.
Examples 8 to 12 each prepared a leatherette paper, which differs from example 7 in that the polyurethane dispersion used was derived from a different source, specifically, the polyurethane dispersion of example 8 was derived from example 2, the polyurethane dispersion of example 9 was derived from example 3, and so on, the polyurethane dispersion of example 12 was derived from example 6.
Comparative example 1
This comparative example prepared a polyurethane dispersion, the specific procedure differed from example 1 by:
(1) step D1 is not included;
(2) in step D3a, alkali lignin is not added;
(3) in step D3c, the resulting polyurethane dispersion had a plant-based content of about 71%.
Comparative example 2
This comparative example prepared a polyurethane dispersion, the specific procedure differed from example 6 by:
(1) step D2 is not included;
(2) in the step D3a, no vegetable oil-based polyol is added;
(2) in step D3c, the resulting polyurethane dispersion had a plant-based content of about 60%.
Comparative example 3
The comparative example prepares a polyurethane dispersion by the specific process of:
C1. uniformly mixing 50 parts of polypropylene glycol (average molecular weight 2000) and 10 parts of BDO, wherein the stirring speed is 250 rpm;
C2. adding 30 parts of isophorone diisocyanate (IPDI, which is a petroleum-based product) and 0.1% by mass of dibutyltin dilaurate, N, to the mixture obtained in step C12Heating and reacting for 5 hours at 70 ℃ in the atmosphere, and stopping when the amount of NCO substance is 5% +/-0.0055% of the addition amount;
C3. adding 10 parts of DMPA and 5ml of acetone into the mixture obtained in the step C2 to reduce the viscosity, controlling the stirring speed at 250rpm, heating and reacting for 2 hours at 70 ℃, and stopping after NCO reaches a theoretical value;
C4. and C, cooling the mixture obtained in the step C3 to 50 ℃, adding 10 parts of TEA to perform neutralization reaction for 50min, adding 200 parts of deionized water, emulsifying and dispersing at a high speed of 3000rpm for 2h, and finally performing rotary evaporation at 40 ℃ to remove the solvent to obtain the aqueous polyurethane dispersion with the solid content of 30%, wherein the content of the plant base is not included.
Comparative example 4
This comparative example prepared a polyurethane dispersion, the specific procedure differed from example 7 by:
the polyurethane dispersion obtained in comparative example 1 was used; meanwhile, the thickness of the coating film is 0.5 mm.
Comparative example 5
This comparative example prepared a polyurethane dispersion, the specific procedure differed from example 7 by:
the polyurethane dispersion obtained in comparative example 3 was used.
Test examples
In the first aspect of this test example, the performance of the polyurethane dispersions prepared in examples 1 to 6 and comparative examples 1 to 3 was tested. The test results are shown in table 1, and the test method is as follows: uniformly pouring the obtained polyurethane dispersion liquid on a polytetrafluoroethylene plate, standing for 2 days at room temperature, then putting into a drying oven, drying for 24 hours at 60 ℃, and stamping into a standard dumbbell test piece;
first, infrared results of the polyurethane dispersion film-forming adhesive film obtained in example 1 and the isocyanate (PDI) film-forming adhesive film used in example 1 were obtained, and the test results are shown in fig. 1. The results show that the characteristic peaks of the isocyanate in the film formed from the polyurethane dispersion disappear or diminish, indicating a substantially complete reaction of the isocyanate.
Then, an INSTRON 3300 material testing machine is adopted to measure the tensile strength and the elongation at break of the adhesive film according to GB/T1040-92; and (3) placing the same mass of adhesive films in the same temperature and humidity environment, carrying out a biological decomposition test according to the measurement of the final aerobic biological decomposition capacity of the material under the standard GB/T19277.1-2011 controlled composting condition, comparing the disintegration rate of the adhesive films after placing for 1 month, judging the decomposition degree, and obtaining the test result shown in table 1.
TABLE 1 Properties of polyurethane dispersions prepared in examples 1 to 6 and comparative examples 1 to 3
As can be seen from Table 1, compared with the glue film formed by the petroleum-based polyurethane dispersion liquid prepared in the example and the comparative example 3, the glue film formed by the polyurethane dispersion liquid prepared in the examples 1-6 (which comprises the plant-based raw material plant oil-based polyol and alkali lignin) has better tensile strength and elongation at break than the comparative example 3, particularly has the disintegration degree of only 23.5 percent in the comparative example 3, while the glue film formed by the polyurethane dispersion liquid prepared in the example has the disintegration degree of more than or equal to 80.5 percent; compared with the traditional petroleum-based polyurethane dispersion liquid, the polyurethane dispersion liquid provided by the invention not only improves the degradability of the polyurethane dispersion liquid to form a glue film, but also improves the mechanical property of the polyurethane dispersion liquid.
Compared with the comparative example 1 without adding the alkali lignin, the tensile strength and the elongation at break are both obviously improved along with the increase of the content of the refined alkali lignin, the maximum tensile strength can reach 38.9MPa which is more than 2 times of that of the refined alkali lignin, and the maximum elongation at break can reach 2480 percent, because the alkali lignin contains a rigid aromatic ring structure, the crosslinking degree and the strength can be obviously improved, and the rebound resilience of the adhesive film is also improved to a certain extent. The tensile strength of the adhesive film is reduced along with the increase of the addition amount of the alkali lignin, because part of the alkali lignin cannot completely react along with the increase of the addition amount of the alkali lignin, and part of the alkali lignin forms independent particles to serve as a filler to be distributed on the surface of the adhesive film, so that the adhesive film is broken due to uneven stress when the adhesive film is subjected to external force. Meanwhile, the mechanical property of the adhesive film formed by the polyurethane dispersion liquid can be effectively improved by adding the alkali lignin in the range provided by the invention. However, the disintegration rates of the example and the comparative example 1 are equivalent, which shows that the selection of the plant-based raw materials is a key factor for improving the degradability of the polyurethane film.
Compared with the comparative example 2 without adding the vegetable oil-based polyol, due to the existence of rigid benzene rings in the alkali lignin, hydroxyl groups in the alkali lignin and isocyanate are subjected to chemical reaction, the crosslinking strength is improved, the strength of the adhesive film is slightly higher than that of the adhesive film in the comparative example 1, but the strength and the elongation at break of the adhesive film are lower than those of the adhesive films in the examples 1-6. The above conclusion for comparative example 1 is confirmed by a disintegration rate of 80% or more: the selection of the plant-based raw materials is a key factor for improving the degradability of the polyurethane adhesive film.
In summary, from the results in table 1, it can be seen that the degradability of the polyurethane film is related to the selection of the plant-based raw materials, and the mechanical properties of the polyurethane film are related to the mutual combination of the components of the plant-based raw materials.
In the second aspect of the test example, the performances of the leatherette papers obtained in examples 7 to 12 and comparative examples 4 to 5 were tested, and the test method was: the tearing degree is tested according to the GB/T455 standard; the burst strength is tested according to the GB/T454 standard, and the reference is made to the GB/T22865-2008 standard for comparison. Wherein the water absorption property is detected according to GB/T1540 standard (water absorption is less than or equal to 30%), and the same amount is 120g/m2The leatherette paper is placed indoors for 48 hours, and the ratio of the weight difference value to the original weight is tested at normal temperature. The test results are shown in table 2.
TABLE 2 Properties of leatherette papers obtained in examples 7 to 12 and comparative examples 4 to 5
As can be seen from Table 2, in comparison with comparative example 5, in comparative example 4, the longitudinal and transverse tear strength and the bursting strength of the leatherette papers prepared in examples 7-12 are higher than those of petroleum-based PU leatherette paper (comparative example 5), which is consistent with the test results of the mechanical properties of the adhesive films in Table 1, and the water absorption levels of the leatherette papers are equivalent. With the increase of the content of alkali lignin in the plant-based polyurethane dispersion liquid, the tearing strength and the bursting strength of the leather-filled paper are obviously enhanced, and the performance is obviously improved. As can be seen from Table 2, the water absorption and air permeability of the leatherette papers prepared in examples 7-12 meet the detection standards, the water absorption of the leatherette papers is reduced with the increase of the content of the alkali lignin, the water absorption of example 9 reaches 0.04%, and is reduced by more than 6 times compared with that of comparative example 4; when the addition amount of the alkali lignin is increased, the water absorption amount is increased again, and it can be expected that if the addition amount of the alkali lignin exceeds the range required by the invention, the water absorption amount of the obtained leatherette paper is difficult to meet the requirement, so the addition amount of the alkali lignin needs to be controlled within a certain range, otherwise, the crosslinked network structure of the adhesive film is damaged. Therefore, the alkali lignin is added in the synthesis process of the plant-based polyurethane dispersion liquid, so that the leatherette paper can achieve high-efficiency waterproof performance and has excellent waterproof performance.
The plant-based biological waterborne polyurethane dispersion liquid prepared by the invention, a thickening agent, a defoaming agent and a leveling agent are prepared into a coating liquid with a certain viscosity according to a proportion, PU leather-filled paper with different patterns and glossiness can be obtained by dry transfer, rolling and polishing processes of release paper, the prepared PU leather-filled paper has good waterproof performance and tearing strength, can meet the requirements of leather-filled paper products, does not influence air permeability, and can be applied to high-grade gift boxes, jewel boxes, cosmetic boxes, photo albums, books and the like.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The polyurethane dispersion is characterized by comprising the following raw materials in parts by weight:
0.5-10 parts of alkali lignin;
30-60 parts of vegetable oil-based polyol;
10-50 parts of isocyanate;
10-40 parts of a chain extender.
2. The polyurethane dispersion according to claim 1, wherein the alkali lignin is prepared by a method comprising the steps of:
A1. adjusting the crude alkali lignin aqueous solution to be alkaline, and removing precipitated impurities;
A2. acid precipitation is carried out on the liquid phase mixture obtained in the step A1;
A3. washing the precipitate obtained in step A2;
preferably, in step A1, the basic pH is 12-14; preferably, the pH of the acid precipitate in the step A2 is 2-3; preferably, step a3 further comprises drying and grinding after the washing.
3. The polyurethane dispersion of claim 1, wherein the vegetable oil based polyol is prepared by a process comprising the steps of:
B1. carrying out epoxidation reaction on vegetable oil under the action of a first acid catalyst and an oxidant;
B2. carrying out ring opening reaction on the product obtained in the step B1 under the action of a second acid catalyst and a ring opening agent to obtain the catalyst;
preferably, in step B1, the mass ratio of the vegetable oil, the first acid catalyst and the oxidizing agent is 100: (1-5): (30-70);
preferably, in the step B2, the mass ratio of the product obtained in the step B1, the second acid catalyst and the ring-opener is 100: (1-5): (10-50).
4. The polyurethane dispersion as claimed in claim 1, wherein the vegetable oil-based polyol has an average molecular weight of 1000-4000; preferably, the isocyanate is selected from diisocyanates; preferably, the diisocyanate is selected from 1, 5-pentamethylene diisocyanate; preferably, the molar ratio of the isocyanate to the vegetable oil-based polyol is (1.5-4): 1.
5. the polyurethane dispersion of claim 1, wherein the chain extender comprises a first chain extender and a second chain extender; preferably, the addition amount of the first chain extender is 5-20 parts by weight; preferably, the first chain extender is selected from at least one of 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, glycerol, triethylene glycol, sorbitol, diethylaminoethanol; preferably, the mass ratio of the addition amount of the alkali lignin to the addition amount of the first chain extender is 1: (1-19); preferably, the addition amount of the second chain extender is 5-20 parts.
6. The polyurethane dispersion according to claim 1, wherein the raw materials for preparing the polyurethane dispersion further comprise at least one of a neutralizing agent, a catalyst, a solvent and water; preferably, the addition amount of the neutralizing agent is 5-20 parts by weight; preferably, the addition amount of the solvent is 10-50 parts by weight; preferably, the addition amount of the water is 100-500 parts.
7. A process for preparing a polyurethane dispersion as claimed in any one of claims 1 to 6, comprising the steps of:
s1, carrying out prepolymerization reaction on the alkali lignin, the vegetable oil-based polyol, a first chain extender and isocyanate;
and S2, adding a second chain extender into the mixture obtained in the step S1, and neutralizing and emulsifying to obtain the polyurethane foam material.
8. The method according to claim 7, wherein in step S1, the temperature of the prepolymerization reaction is 60-80 ℃; preferably, in the step S1, the time of the prepolymerization reaction is 2-6 hours; preferably, in the step S2, the neutralization temperature is 0-50 ℃; preferably, the neutralization time is 0.5-2 h; preferably, in the step S2, the emulsifying time is 1-4 h; preferably, the emulsification is achieved by stirring; preferably, the rotation speed of the stirring is 2000-.
9. A leatherette paper which is characterized in that a preparation raw material comprises a leatherette paper pulp, and the preparation raw material of the leatherette paper pulp comprises the polyurethane dispersion liquid as claimed in any one of claims 1 to 6.
10. The method for preparing the leatherette paper as claimed in claim 9, which comprises coating the leatherette paper pulp on the surface of a paper substrate, and sequentially performing drying, matte treatment and surface post-treatment.
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