CN113527611B - 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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- CN113527611B CN113527611B CN202110861430.2A CN202110861430A CN113527611B CN 113527611 B CN113527611 B CN 113527611B CN 202110861430 A CN202110861430 A CN 202110861430A CN 113527611 B CN113527611 B CN 113527611B
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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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- 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. There was an investigation that the global polyurethane mass reached 2120 million t in 2016, while it was estimated that 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, renewable resources such as alkali lignin and vegetable oil-based polyol derived from plants are used as main film forming substances of the polyurethane dispersion liquid, so that the stress of shortage of petroleum resources can be relieved; 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. performing acid precipitation on the liquid phase mixture obtained in the step A1;
A3. and (3) 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 the step A1, the mass percentage of the crude alkali lignin in the aqueous crude alkali lignin solution is 20-50%.
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 about 30%.
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 an aqueous solution of sodium hydroxide with a mass concentration of 5 to 10%.
In some embodiments of the invention, in step A1, the basic pH is from 12 to 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 10-30min.
In some embodiments of the invention, the stirring is for about 15min. 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 the step A2, the acid precipitation is performed by using 10 to 20% by weight of hydrochloric acid.
In some embodiments of the present invention, in step A2, the acid is precipitated by using hydrochloric acid with a mass percentage of about 12%.
In some embodiments of the invention, in step A2, the pH of the acid precipitate is 2 to 3.
In some embodiments of the invention, the temperature of the acid precipitation in step A2 is 60 to 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 said washing.
In some embodiments of the invention, in step A3, the temperature of the drying after washing is 60 to 80 ℃.
In some embodiments of the present 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 to 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 method of 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. c, 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 to 70).
In some embodiments of the invention, the temperature of the epoxidation reaction in step B1 is in the range of from 40 to 80 ℃.
In some embodiments of the invention, in step B1, the epoxidation reaction is carried out for a period of time ranging from 5 to 10 hours.
In some embodiments of the invention, in step B1, the epoxidation reaction is carried out for a period of time ranging from 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 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 meanwhile, 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 obtained in step B1, the second acid catalyst and the ring-opener is 100: (1-5): (10 to 50).
In some embodiments of the invention, in step B2, the temperature of the ring-opening reaction is between 80 and 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 is carried out for a period of 2 to 6 hours.
In some embodiments of the invention, in step B2, the ambient pressure of the ring-opening reaction is between 0.1 and 0.5MPa.
In some embodiments of the invention, in step B2, the ambient pressure of the ring-opening reaction is about 0.3MPa.
In some embodiments of the present invention, the raw materials for preparing the polyurethane dispersion include 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 present 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 70wt% is from plants, that is, the biobased content of the 1, 5-pentamethylene diisocyanate is 70wt%.
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 to 19).
In some embodiments of the 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 to 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 invention, in step S1, the prepolymerization is carried out over the catalyst.
In some embodiments of the invention, the mass of the catalyst added is 0.02-0.2% of the mass of the reaction film-forming material in the 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 invention, the mass of the catalyst added 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 needs to be subjected to air-isolated treatment with an isolation gas.
In some embodiments of the present invention, the temperature of the prepolymerization reaction in step S1 is 60 to 80 ℃.
In some embodiments of the present invention, the temperature of the prepolymerization reaction in step S1 is 70 to 80 ℃.
In some embodiments of the invention, in step S1, the temperature of the prepolymerization is carried out by means of an oil bath.
In some embodiments of the present invention, in step S1, the prepolymerization time is 2 to 6 hours.
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 carried out under stirring.
In some embodiments of the present invention, the stirring speed of the prepolymerization reaction is 120 to 300rpm.
In some embodiments of the present invention, the stirring speed of the prepolymerization reaction is 200 to 300rpm.
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 is stopped, i.e., 80-90% of the isocyanate in the amount of material is reacted.
In some embodiments of the invention, the reaction temperature after the addition of the second chain extender in step S2 is 40 to 80 ℃.
In some embodiments of the invention, the reaction temperature after the addition of the second chain extender in step S2 is about 70 ℃.
In some embodiments of the 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 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 to 300rpm.
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 250rpm.
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 groups is 5 to 15% of the molar amount of the isocyanate groups 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 added simultaneously with the second chain extender in step S2; 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 invention, the temperature of the neutralization in step S2 is 0 to 50 ℃.
In some preferred embodiments of the present invention, the temperature of the neutralization in step S2 is about 50 ℃.
In some embodiments of the invention, in step S2, the time for neutralization is 0.5 to 2 hours.
In some embodiments of the invention, the time for neutralization in step S2 is about 50min.
In some embodiments of the present invention, in step S2, the water is added during the emulsification.
In some embodiments of the invention, the time for the emulsification in step S2 is 1 to 4 hours.
In some embodiments of the invention, the time for the emulsification in step S2 is about 2h.
In some embodiments of the invention, the emulsification is achieved by stirring.
In some embodiments of the invention, the rotation speed of the stirring in the emulsification is 2000-8000rpm.
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 a 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 isolation 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 preparation raw materials of the leatherette paper prepared by the invention comprise the polyurethane dispersion liquid, the main raw materials are from plants and are abundant in source, the obtained leatherette paper is degradable, environment-friendly and non-toxic, the problems that the traditional leatherette paper is toxic and has pungent smell are solved, and the invention 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 invention, the rotational speed of centrifugation for the centrifugal debubbling is 3000-8000rpm.
In some preferred embodiments of the present invention, the rotational speed of the centrifugal debubbling is about 3000rpm.
In some embodiments of the invention, the centrifugation time for the centrifugal debubbling is 10 to 30min.
In some preferred embodiments of the present invention, the centrifugation time for the centrifugal debubbling is about 15min.
In some embodiments of the invention, the time of standing is 5-30min.
In some embodiments of the invention, in the method of making the leathered paper, the coating has a thickness of 0.1 to 1mm.
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 1mm.
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 then filtering;
d1d, reversely washing the filter residue used in the step D1c with deionized water until the pH value of the filtrate is neutral, then putting the filter residue into a 60 ℃ drying 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 0.3MPa;
D3. preparation of polyurethane dispersion:
d3a, adopting a prepolymerization method, uniformly mixing 0.5 part of refined alkali lignin, 50 parts of bio-based polyol and 9.5 parts of BDO (first chain extender) which are dissolved in 10% acetone in mass fraction of a reaction film forming material according to a certain mass fraction ratioMixing at a stirring rate of 250rpm, then adding 30 parts by weight of PDI and 0.1% by mass (i.e. 0.1 g) of dibutyltin dilaurate (catalyst) based on the mass fraction of film-forming substances in N 2 Heating and reacting for 5h at 70 ℃ in the atmosphere, and stopping when the amount of NCO substance is 10 +/-0.011 percent 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 for emulsification and dispersion 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 BDO is 9 parts by weight;
(2) In step D3c, the plant-based content of the polyurethane dispersion obtained is 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 plant-based content of the polyurethane dispersion obtained is 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 plant-based content of the polyurethane dispersion obtained is about 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 plant-based content of the polyurethane dispersion obtained is about 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 has 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, EPP 112), 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, blade-coating the leather-covered paper pulp obtained in the step E1 on the surface of a paper base, wherein the coating thickness is 0.5mm, and obtaining the leather-covered paper through hot air drying at 80 ℃, calendaring and embossing.
Examples 8 to 12 each prepared a leathery paper, differing in particular from example 7 in the source of the polyurethane dispersion used, in particular, 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) Not comprising step D1;
(2) In the step D3a, alkali lignin is not added;
(3) In step D3c, the plant-based content of the polyurethane dispersion obtained is about 71%.
Comparative example 2
This comparative example prepared a polyurethane dispersion, the specific procedure differed from example 6 by:
(1) Not including step D2;
(2) In the step D3a, no vegetable oil-based polyol is added;
(2) In step D3c, the plant-based content of the polyurethane dispersion obtained is 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 250rpm;
C2. adding 30 parts of isophorone diisocyanate (IPDI, which belongs to petroleum-based products) and dibutyltin dilaurate with a total reaction mass fraction of 0.1%, N, to the mixture obtained in the step C1 2 Heating and reacting for 5h 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 at 70 ℃ for 2 hours, and stopping when 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, performing high-speed emulsification and dispersion for 2h at 3000rpm, and finally performing rotary evaporation at 40 ℃ to remove the solvent to obtain the waterborne polyurethane dispersion liquid 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 0.5mm.
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 an oven, drying for 24 hours at 60 ℃, and stamping into a standard dumbbell test piece;
first, infrared results of the adhesive film formed from the polyurethane dispersion obtained in example 1 and the adhesive film formed from the isocyanate (PDI) 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 controlled composting condition of the standard GB/T19277.1-2011, comparing the disintegration rate of the adhesive films after placing for 1 month, and judging the decomposition degree, wherein the test results are 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 comparative example 3, the glue films formed by the polyurethane dispersion liquids prepared in the examples 1-6 (which comprise plant-based raw material vegetable oil-based polyol and alkali lignin) have better tensile strength and elongation at break than the comparative example 3, especially the disintegration degree, the disintegration degree of the comparative example 3 is only 23.5%, while the glue film formed by the polyurethane dispersion liquid prepared in the examples has the disintegration degree of more than or equal to 80.5%; 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 comparative example 2 without adding 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 comparative example 1, but the strength and the elongation at break of the adhesive film are lower than those of examples 1 to 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 a second aspect of this test example, the properties of the leathered papers obtained in examples 7 to 12 and comparative examples 4 to 5 were tested by: the tearing degree is tested according to the GB/T455 standard; the burst strength is tested according to the GB/T454 standard, and the control is carried out according to the GB/T22865-2008 standard. 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/m 2 The 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 leathers 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, the leatheroid papers prepared in examples 7 to 12 had higher tear strength and bursting strength in both the longitudinal and transverse directions than the petroleum-based PU leatheroid paper (comparative example 5), which are consistent with the test results of mechanical properties of the adhesive film in Table 1, and the water absorption levels of the leatheroid papers are equivalent to those of comparative example 4. 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 drawings, but the present invention is not limited to the 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 (17)
1. The leather-covered paper is characterized in that the raw materials for preparing the leather-covered paper comprise leather-covered paper pulp, the raw materials for preparing the leather-covered paper pulp comprise polyurethane dispersion liquid, and the raw materials for preparing the polyurethane dispersion liquid comprise the following components in parts by weight:
0.5 to 10 portions of alkali lignin;
30 to 60 parts of vegetable oil-based polyol;
10-50 parts of isocyanate;
5-20 parts of a first chain extender;
5-20 parts of a second chain extender;
the preparation method of the alkali lignin comprises the following steps:
A1. adjusting the crude alkali lignin aqueous solution to be alkaline, and removing precipitated impurities;
A2. carrying out acid precipitation on the liquid phase mixture obtained in the step A1;
A3. washing the precipitate obtained in the step A2;
the preparation method of the vegetable oil-based polyol comprises the following steps:
B1. carrying out epoxidation reaction on vegetable oil under the action of a first acid catalyst and an oxidant;
B2. c, 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 the step B1, the mass ratio of the vegetable oil, the first acid catalyst and the oxidant is 100: (1 to 5): (30 to 70);
in the step B2, the mass ratio of the product obtained in the step B1 to the second acid catalyst to the ring-opener is 100: (1 to 5): (10 to 50);
the average molecular weight of the vegetable oil-based polyol is 1000 to 4000;
the vegetable oil is linseed oil;
the isocyanate is selected from 1, 5-pentamethylene diisocyanate;
the molar ratio of the isocyanate to the vegetable oil-based polyol is (1.5 to 4): 1;
the first chain extender is selected from at least one of 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol and triethylene glycol;
according to weight percentage, the mass ratio of the addition amount of the alkali lignin to the addition amount of the first chain extender is 1: (1 to 19);
the second chain extender is selected from DMPA.
2. The leatherette paper according to claim 1, wherein in the step A1, the alkaline pH is 12 to 14.
3. The leatherette paper according to claim 1, wherein the pH of the acid precipitation in the step A2 is 2 to 3.
4. The leathered paper of claim 1, further comprising drying and grinding after the washing in step A3.
5. The leathered paper according to claim 1, wherein the polyurethane dispersion is prepared from a raw material further comprising at least one of a neutralizer, a catalyst, a solvent and water.
6. The leatherette paper as claimed in claim 5, wherein the neutralizer is added in an amount of 5 to 20 parts by weight.
7. The leatherette paper as claimed in claim 5, wherein the solvent is added in an amount of 10 to 50 parts by weight.
8. The leatherette paper as claimed in claim 5, wherein the water is added in an amount of 100 to 500 parts.
9. The leatherette paper as claimed in claim 1, wherein the polyurethane dispersion is prepared by a method 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.
10. The leatherette paper as claimed in claim 9, wherein in step S1, the temperature of the prepolymerization reaction is 60-80 ℃.
11. The leatherette paper as claimed in claim 9, wherein in step S1, the prepolymerization reaction time is 2-6h.
12. The leatherette paper according to claim 9, wherein the temperature of the neutralization in the step S2 is 0-50 ℃.
13. The leather-filled paper according to claim 9, wherein the neutralization time is 0.5 to 2h.
14. The leatherette paper according to claim 9, wherein the emulsification time in step S2 is 1 to 4h.
15. The leathered paper of claim 9, wherein the emulsification is achieved by agitation.
16. The leatherette paper as claimed in claim 15, wherein the stirring speed is 2000-8000rpm.
17. The method for preparing the leather-filled paper according to any one of claims 1 to 16, wherein the leather-filled paper pulp is coated on the surface of a paper substrate, and the paper substrate is dried, matte and subjected to surface post-treatment in sequence.
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