CN106349448A - Biologic water-based polyurethane and preparation method thereof - Google Patents
Biologic water-based polyurethane and preparation method thereof Download PDFInfo
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- CN106349448A CN106349448A CN201610778952.5A CN201610778952A CN106349448A CN 106349448 A CN106349448 A CN 106349448A CN 201610778952 A CN201610778952 A CN 201610778952A CN 106349448 A CN106349448 A CN 106349448A
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
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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
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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
- C08G2230/00—Compositions for preparing biodegradable polymers
Abstract
The invention discloses biologic water-based polyurethane and a preparation method of biologic water-based polyurethane, and belongs to the technical field of water-based polyurethane emulsion. The preparation method comprises the steps of preparing polylactic acid polyol by taking lactic acid as a raw material, and allowing polylactic acid polyol to react with isocyanate and hydrophilic chain extender to prepare biologic water-based polyurethane. The preparation method is simple and practicable; prepared water-based polyurethane has a higher solid content, excellent storage stability, relatively low film-forming temperature and excellent mechanical and optical properties after film formation; at the same time, polylactic acid polyol is adopted to substitute petroleum based polymer polyol; the production cost is lowered; an obtained object product has excellent biodegradability at the same time; the problem of environmental pollution caused by waste is solved.
Description
Technical field
The invention belongs to aqueous polyurethane emulsion technical field, specifically belong to a kind of biology base water polyurethane and its system
Preparation Method.
Background technology
Polyurethane is a kind of multifunctional macromolecule material, and raw material variety is various, molecular structure scalable, has higher gluing
Knotting strength, the advantages of excellent resistance to impact, lower temperature resistance and rub resistance, is widely used in coating, adhesive, leather finish
The fields such as agent, ink.Common solvent type polyurethane is with acetone, butanone, ethyl acetate, ethyl acetate, dimethylformamide etc.
For primary organic solvent, but these organic solvents are all inflammable, explosive, poisonous hazardous chemicals.In use, it is simultaneously
Adjust viscosity it is ensured that good serviceability, general polyurethane also can use the organic solvents such as toluene, for related work people
The health of member damages.
Aqueous polyurethane emulsion is to replace organic solvent as disperse medium using water, has nontoxic, pollution-free, environmental protection, honest and clean
The advantages of valency, receive the attention of more and more people, and obtained extensively in fields such as adhesive, coating, leather finish, ink
General application.
Chinese invention patent application (application publication number: cn105732928a, Shen Qing Publication day: 2016-07-06) discloses
A kind of preparation method of biomass-based aqueous polyurethane, polyhydric alcohol is placed in by this preparation method with biomass liquefying product mixture
Have in the there-necked flask of temperature control, stirring and condensing units, add diisocyanate and catalyst, after reaction, obtain material a；Obtaining
Material a in add hydrophilic chain extender carry out chain extending reaction, obtain biomass-based waterborne polyurethane prepolymer；In the biomass obtaining
Add acetone soln adjustment viscosity in base water polyurethane prepolymer, add salt-forming reagent to be neutralized reaction after reaction, cooling
Add deionized water dispersion to room temperature, recycle revolving to remove the acetone in aqueous solution, obtain final product biomass-based aqueous polyurethane.
It is an advantage of the invention that biomass adopt agriculture and forestry organic waste material, reduce production cost, shortcoming is that the solid content of emulsion is low.
Polylactic acid multi-element alcohol is a kind of biodegradable thermoplastic aliphatic's PEPA of synthetic, mainly former
Material lactic acid is Renewable resource again, and its nontoxic, nonirritant has a good biocompatibility, biodegradable absorption, finally
Complete biodegradable is carbon dioxide and water, and mechanical strength is high, free from environmental pollution, plasticity good it is easy to machine-shaping, have extensively
General research and application prospect, meet the strategy of sustainable development advocated now, are acknowledged as the most promising life of new century
One of thing medical material and new packaging material.In the face of the petroleum resources of increasingly depleted, the application of polylactic acid and its derivant is opened
Send out research, contribute to variation, environmental protection and renewableization of new polyurethane raw materials, widen answering of polyurethane material
Use field.
Content of the invention
For solving above-mentioned technical problem, it is an object of the invention to disclosing a kind of biology base water polyurethane and its preparation
Method.With biological poly lactic acid polyhydric alcohol as raw material, part replaces petroleum base polymer polyatomic alcohol to the present invention, and the aqueouss of preparation are gathered
Urethane has outstanding bin stability, excellent mechanics and optical property after relatively low film-forming temperature and film forming.
The invention discloses a kind of preparation method of biology base water polyurethane, comprise the following steps:
1) prepare polylactic acid multi-element alcohol: lactic acid, small molecule dihydroxylic alcohols and catalyst a are reacted under inert gas conditions,
Prepare polylactic acid multi-element alcohol；
2) prepare base polyurethane prepolymer for use as: described step 1) the polylactic acid multi-element alcohol prepared with isocyanates in noble gases bar
React under part, be subsequently adding catalyst b and carry out catalytic reaction, prepare base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add in the base polyurethane prepolymer for use as prepared and contain hydrophilic group two
First alcohol carries out first time chain extending reaction, adds triethylamine and is neutralized reaction, after adding deionized water to carry out emulsifying, adds and expands
Chain agent carries out second chain extending reaction, prepares biological base water polyurethane.
Further, described catalyst a be zinc Isoocatanoate, isooctyl acid bismuth, dibutyl tin laurate, stannous octoate, two
In acetic acid butyl tin, tetrabutyl titanate and tetraisopropyl titanate one or more.
Yet further, described catalyst b is stannous octoate, stannous oleate, dibutyltin dilaurate, propanoic acid phenyl
One of hydrargyrum and lead octoate or more than one.
Further, described small molecule dihydroxylic alcohols be propylene glycol, ethylene glycol, bis-phenol a, bis-phenol s, BDO, new
One of pentanediol and diglycol.
Further, isocyanates be methylene diisocyanate, 4,4'- methylene two carbanil, to benzene two
Isocyanates, trimethyl hexamethylene diisocyanate, dimethyl diphenyl diisocyanate, O-phthalic group diisocyanate,
In 2,4 tolylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride diisocyanate
One or more.
Further, described dihydroxylic alcohols containing hydrophilic group are one of dihydromethyl propionic acid, dimethylolpropionic acid or two
Kind.
Further, described chain extender is ethylenediamine, BDO, ethylene glycol, neopentyl glycol, a contracting diethyl two
In alcohol, trimethylolpropane one or more.
Further, the hydroxyl value of described polylactic acid multi-element alcohol is 28～224mg koh/g, and acid number is less than or equal to 2mg
koh/g.
The invention also discloses a kind of biology base water polyurethane, described biology base water polyurethane is according to above-mentioned biology
The preparation method of base water polyurethane prepares.
The present invention adopts the lactic acid of bio-based is raw material, by polylactic acid multi-element alcohol and isocyanates, hydrophilic chain extender
Reaction, prepares biological base water polyurethane, compared with prior art has the advantages that
1st, petroleum base polymer polyatomic alcohol can partly be replaced using polylactic acid multi-element alcohol, not only reduce production cost,
The target product simultaneously prepared has excellent biological degradability, solves the problem of environmental pollution that garbage causes.
2nd, the biological base water polyurethane of present invention preparation has an outstanding bin stability, relatively low film forming temperature
Degree, and there is after film forming excellent mechanical property and optical property, expand the application of aqueous polyurethane.
3rd, the preparation method of the present invention is simple, and the aqueous polyurethane solid content of preparation is higher, between 30～60%.
Brief description
Fig. 1 is the process chart of preparation method of the present invention.
Specific embodiment
For solving the technical problem of the present invention, the invention provides first technical scheme:
The invention discloses a kind of preparation method of biology base water polyurethane, comprise the following steps:
1) prepare polylactic acid multi-element alcohol: add small molecule dihydroxylic alcohols and catalyst a in lactic acid, controlling reaction temperature is
120～160 DEG C, under nitrogen protective condition, react 3～5h, then keep reaction temperature constant, evacuation 0.5～1h, it is prepared into
To polylactic acid multi-element alcohol.
Preferably, small molecule dihydroxylic alcohols are less than or equal to 12 dihydroxylic alcohols for carbon number.
It is further preferred that small molecule dihydroxylic alcohols be propylene glycol, ethylene glycol, BDO, neopentyl glycol and one contracting two
One of ethylene glycol.
It is further preferred that small molecule glycol is BDO.
Preferably, catalyst a be one of zinc class catalyst, tin catalyst and titanate ester catalyst or one kind with
On.
It is further preferred that catalyst a be zinc Isoocatanoate, isooctyl acid bismuth, dibutyl tin laurate, stannous octoate, two
In acetic acid butyl tin, tetrabutyl titanate and tetraisopropyl titanate one or more.
It is further preferred that catalyst a is stannous octoate and tetrabutyl titanate, and mass ratio is 1:1.
Preferably, the quality of small molecule dihydroxylic alcohols is the 40～60% of lactic acid quality, and the quality of catalyst a is small molecule two
First alcohol and the 0.005%～0.02% of lactic acid gross mass.
It is further preferred that the quality of small molecule dihydroxylic alcohols is the 47% of lactic acid quality, the quality of catalyst a is small molecule
Dihydroxylic alcohols and the 0.01% of lactic acid gross mass.
2) prepare base polyurethane prepolymer for use as: polylactic acid multi-element alcohol and isocyanates, under nitrogen protective condition, control reaction temperature
Spend for 50～110 DEG C, stirring reaction 0.5～5h, then controlling reaction temperature be 50～80 DEG C, add catalyst b, react 0.5
～3h, prepares base polyurethane prepolymer for use as.
Preferably, catalyst b is stannous octoate, stannous oleate, dibutyltin dilaurate, phenyl mercury propionate and octanoic acid
One of lead or more than one.
It is further preferred that catalyst b is stannous octoate and dibutyltin dilaurate.
Preferably, isocyanates be methylene diisocyanate, 4,4'- methylene two carbanil, to benzene two isocyanide
Acid esters, trimethyl hexamethylene diisocyanate, dimethyl diphenyl diisocyanate, O-phthalic group diisocyanate, 2,4-
In toluene-2,4-diisocyanate, naphthalene diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride diisocyanate one
Plant or more than one.
It is further preferred that isocyanates are isophorone diisocyanate and toluene di-isocyanate(TDI).
It is further preferred that isocyanate index is 1.1～2.0, the quality of catalyst b is that isocyanates are many with polylactic acid
The 0.05～0.3% of first alcohol gross mass.
And the hydroxyl value of described polylactic acid multi-element alcohol is 28～224mg koh/g, acid number is less than or equal to 2mg koh/g.
3) prepare biological base water polyurethane: in base polyurethane prepolymer for use as, add dihydroxylic alcohols containing hydrophilic group to carry out first time chain extension
Reaction, reaction temperature is 70～80 DEG C, and the response time is 0.5～1h, is subsequently adding acetone and adjusts viscosity, reaction temperature is reduced
To 25～35 DEG C, add triethylamine and be neutralized reaction, react 5～15min, after adding deionized water to carry out emulsifying, add
Chain extender carries out second chain extending reaction, stirring reaction 10～30min, then reduces pressure and slough acetone, prepares bio-based aqueouss
Polyurethane, the solid content of biological base water polyurethane is between 30～60%.
Preferably, dihydroxylic alcohols containing hydrophilic group are one of dihydromethyl propionic acid, dimethylolpropionic acid or two kinds.
Preferably, chain extender is ethylenediamine, BDO, ethylene glycol, neopentyl glycol, diglycol, three hydroxyl first
In base propane one or more.
Technology as the present invention is preferred, and chain extender is ethylenediamine, and the quality of ethylenediamine is polylactic acid multi-element alcohol quality
1.3～3.8%.
Preferably, the quality containing hydrophilic group dihydroxylic alcohols is the 3～12% of polyurethane prepolymer weight, and the quality of triethylamine is
The 2.5～3.5% of polylactic acid multi-element alcohol, isocyanates and the gross mass of dihydroxylic alcohols containing hydrophilic group, the quality of chain extender is polylactic acid
The 1.3～3.8% of polyol quality.
The invention provides second technical scheme is to disclose a kind of biology base water polyurethane.
In order to preferably explain the present invention, it is further elucidated with the main contents of the present invention below in conjunction with specific embodiment, but
Present disclosure is not limited solely to following examples.
The producer source of the raw material that the present embodiment is selected:
Lactic acid: hwg00129, Beijing Chemical Co., Ltd. of Hua Weirui section, BDO: l03491, AlfaAesar (in
State) Chemical Co., Ltd., isophorone diisocyanate: desmodur i, German bayer company, stannous octoate: dabco t-
9, Air Prod ＆ Chem of the U.S., acetone: ar, Chemical Reagent Co., Ltd., Sinopharm Group, dimethylolpropionic acid: ar, Shanghai
Riel chemical technology company limited advanced in years, triethylamine: ar, Shanghai Aladdin biochemical technology limited company, ethylenediamine: ar, on
Sea steps riel chemical technology company limited.
Embodiment 1
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
141g BDO and 0.021g zinc Isoocatanoate, controlling reaction temperature is 120 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
55.8mg koh/g, acid number is 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 2.9g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.4, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, and stirring reaction 3h, then by reaction temperature
It is reduced to 75 DEG C, adds 0.0065g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 0.3870g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3322 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 30%.
Embodiment 2
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
120g propylene glycol and 0.042g zinc Isoocatanoate, controlling reaction temperature is 140 DEG C, reacts 4h, then keep under nitrogen protective condition
Reaction temperature is constant, evacuation 0.5h, prepares polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
40.8mg koh/g, acid number is 0.72mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared is different with 3.34g methylene two
Cyanate is placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylated material in reaction system
Amount ratio be 1.3, under nitrogen protective condition, controlling reaction temperature be 80 DEG C, stirring reaction 3h, then reaction temperature is dropped
As little as 75 DEG C, add 0.0067g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare poly-
Urethane performed polymer；
3) prepare biological base water polyurethane: to described step 2) add 0.4003g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3436 triethylamine and be neutralized reaction, reaction
10min, after adding 33ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 30%.
Embodiment 3
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
132g ethylene glycol and 0.048g isooctyl acid bismuth, controlling reaction temperature is 150 DEG C, reacts 4h, then keep under nitrogen protective condition
Reaction temperature is constant, evacuation 0.5h, prepares polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
38.6mg koh/g, acid number is 0.68mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.79g 4,4 '-methylene
Base two carbanil is placed in there-necked flask it is ensured that isocyanates number, that is, in reaction system the amount of NCO material with
The ratio of the amount of hydroxylated material is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, stirring reaction 3h, then will be anti-
Answer temperature to be reduced to 75 DEG C, add 0.00645g catalyst phenyl mercury propionate, react 2h, add appropriate acetone and adjust and glue
Degree, prepares base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 0.4137g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3550 triethylamine and be neutralized reaction, reaction
10min, after adding 34ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 30%.
Embodiment 4
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
145g neopentyl glycol and 0.055g dibutyl tin laurate, controlling reaction temperature is 160 DEG C, reacts under nitrogen protective condition
3h, then keeps reaction temperature constant, and evacuation 0.5h prepares polylactic acid multi-element alcohol, and polylactic acid multi-element alcohol is detected
Hydroxyl value be 50.8mg koh/g, acid number be 0.52mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared with 3.34g to benzene two isocyanide
Acid esters is placed in there-necked flask it is ensured that isocyanates number, i.e. the amount of NCO material and hydroxylated material in reaction system
The ratio of amount is 1.1, and under nitrogen protective condition, controlling reaction temperature is 110 DEG C, and then reaction temperature is dropped by stirring reaction 1h
As little as 50 DEG C, add 0.0241g octoate catalyst stannous, react 3h, add appropriate acetone and adjust viscosity, prepare poly-
Urethane performed polymer；
3) prepare biological base water polyurethane: to described step 2) add 0.4003g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethyl propionic acid carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3436 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g ethylene glycol to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 60%.
Embodiment 5
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
141g BDO and 0.042g stannous octoate, controlling reaction temperature is 140 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
55.8mg koh/g, acid number is 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared is sub- with 3.34g trimethyl six
Methyl diisocyanate is placed in there-necked flask it is ensured that isocyanates number, that is, in reaction system the amount of NCO material with
The ratio of the amount of hydroxylated material is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, stirring reaction 3h, then will be anti-
Answer temperature to be reduced to 75 DEG C, add 0.0414g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, system
Standby obtain base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 0.4003g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3436 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 55.4%.
Embodiment 6
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
141g BDO and 0.042g zinc Isoocatanoate, controlling reaction temperature is 140 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
55.8mg koh/g, acid number is 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.34g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.1, and under nitrogen protective condition, controlling reaction temperature is 100 DEG C, stirring reaction 3h, then will react temperature
Degree is reduced to 60 DEG C, adds 0.0240g octoate catalyst lead, reacts 2h, adds appropriate acetone and adjusts viscosity, prepares
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.0675 dihydroxies in the base polyurethane prepolymer for use as prepared
Methylbutanoic acid carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts viscosity,
After chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3603 triethylamine and be neutralized reaction, react 10min,
After adding 36ml deionized water to carry out emulsifying, 0.16g ethylenediamine is added to carry out second chain extending reaction, high-speed stirred is reacted
20min, reactant mixture is transferred in round-bottomed flask, is that under -0.08mpa, rotary heating, to 55 DEG C, sloughs third in vacuum
Ketone, prepares the biological base water polyurethane that solid content is 30%.
Embodiment 7
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
141g BDO and 0.042g oxalic acid butyl tin, controlling reaction temperature is 140 DEG C, reacts 5h under nitrogen protective condition,
Then keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl of polylactic acid multi-element alcohol is detected
It is worth for 55.8mg koh/g, acid number is 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.34g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.1, and under nitrogen protective condition, controlling reaction temperature is 90 DEG C, and stirring reaction 3h, then by reaction temperature
It is reduced to 75 DEG C, adds 0.0240g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.6013g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3736 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g trimethylolpropane to carry out second chain extending reaction, at a high speed
Stirring reaction 20min, reactant mixture is transferred in round-bottomed flask, is rotary heating to 55 under -0.08mpa in vacuum
DEG C, slough acetone, prepare the biological base water polyurethane that solid content is 36%.
Embodiment 8
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
150g BDO and 0.042g zinc Isoocatanoate, controlling reaction temperature is 140 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
60.2mg koh/g, acid number is 0.40mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.34g dimethyl diphenyl
Diisocyanate is placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxyl in reaction system
The ratio of the amount of material is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, stirring reaction 3h, then will react temperature
Degree is reduced to 75 DEG C, adds 0.0240g octoate catalyst stannous, reacts 2h, adds appropriate acetone and adjusts viscosity, is prepared into
To base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.0675g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3436 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 31.5%.
Embodiment 9
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
155g BDO and 0.042g zinc Isoocatanoate, controlling reaction temperature is 140 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
61.3mg koh/g, acid number is 0.43mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.34g O-phthalic base
Diisocyanate is placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxyl in reaction system
The ratio of the amount of material is 1.1, and under nitrogen protective condition, controlling reaction temperature is 50 DEG C, stirring reaction 3h, adds 0.0240g
Catalyst dibutyltin dilaurate, reacts 2h, adds appropriate acetone and adjusts viscosity, prepares polyurethane prepolymer
Body；
3) prepare biological base water polyurethane: to described step 2) add 1.0675g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.4323 triethylamine and be neutralized reaction, reaction
10min, after adding 45ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 44%.
Embodiment 10
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
160g BDO and 0.042g tetraisopropyl titanate, controlling reaction temperature is 140 DEG C, reacts 5h under nitrogen protective condition,
Then keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl of polylactic acid multi-element alcohol is detected
It is worth for 65.2mg koh/g, acid number is 0.44mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.34g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, and stirring reaction 3h, then by reaction temperature
It is reduced to 75 DEG C, adds 0.0240g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.0675g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3891 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.13g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 38%.
Embodiment 11
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
162g BDO and 0.042g zinc Isoocatanoate, controlling reaction temperature is 140 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
63.1mg koh/g, acid number is 0.42mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.34g dicyclohexyl first
Alkane diisocyanate is placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxyl in reaction system
The ratio of the amount of substratess matter is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, and then stirring reaction 3h will react
Temperature is reduced to 75 DEG C, adds 0.0240g octoate catalyst stannous, reacts 2h, adds appropriate acetone and adjusts viscosity, preparation
Obtain base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.0675g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3891 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.38g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 30%.
Embodiment 12
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
141g BDO and 0.042g zinc Isoocatanoate, controlling reaction temperature is 140 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
55.8mg koh/g, acid number is 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.34g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, and stirring reaction 3h, then by reaction temperature
It is reduced to 75 DEG C, adds 0.0240g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.0675g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3891 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 40%.
Embodiment 13
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
141g BDO and 0.042g stannous octoate, controlling reaction temperature is 140 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
55.8mg koh/g, acid number is 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 3.34g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, and stirring reaction 3h, then by reaction temperature
It is reduced to 75 DEG C, adds 0.0240g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.0675g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3891 triethylamine and be neutralized reaction, reaction
10min, after adding 60ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 30%.
Embodiment 14
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
141g BDO and 0.042g stannous octoate, controlling reaction temperature is 120 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
55.8mg koh/g, acid number is 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 2.62g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, and stirring reaction 3h, then by reaction temperature
It is reduced to 75 DEG C, adds 0.0240g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.0096g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3680 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 30%.
Embodiment 15
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
The mixture (both mass ratioes are 1:1) of 141g BDO and 0.042g stannous octoate and tetrabutyl titanate, controls anti-
Answer temperature to be 120 DEG C, under nitrogen protective condition, react 5h, then keep reaction temperature constant, evacuation 0.5h, prepare poly-
Lactic acid polyhydric alcohol, and detect polylactic acid multi-element alcohol hydroxyl value be 55.8mg koh/g, acid number be 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 1.08g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.1, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, and stirring reaction 3h, then by reaction temperature
It is reduced to 75 DEG C, adds 0.0199g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 0.8862g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.3230 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 30%.
Embodiment 16
1) prepare polylactic acid multi-element alcohol: in the there-necked flask of 500ml, add 300g lactic acid, then add in lactic acid
141g BDO and 0.042g zinc Isoocatanoate, controlling reaction temperature is 120 DEG C, reacts 5h, then under nitrogen protective condition
Keep reaction temperature constant, evacuation 0.5h, prepare polylactic acid multi-element alcohol, and the hydroxyl value of polylactic acid multi-element alcohol is detected and be
55.8mg koh/g, acid number is 0.46mg koh/g；
2) prepare base polyurethane prepolymer for use as: take step 1 described in 10g) the polylactic acid multi-element alcohol prepared and 5.23g isophorone two
Isocyanates are placed in there-necked flask it is ensured that isocyanates number, the i.e. amount of NCO material and hydroxylic species in reaction system
The ratio of the amount of matter is 1.5, and under nitrogen protective condition, controlling reaction temperature is 80 DEG C, and stirring reaction 3h, then by reaction temperature
It is reduced to 75 DEG C, adds 0.0274g octoate catalyst stannous, react 2h, add appropriate acetone and adjust viscosity, prepare
Base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add 1.2187g bis- in the base polyurethane prepolymer for use as prepared
Hydroxymethylbutyrate carries out first time chain extending reaction, and reaction temperature is 75 DEG C, and the response time is 1h, is subsequently adding acetone and adjusts and glues
Degree, after chain extending reaction terminates, reaction temperature is reduced to 30 DEG C, adds 0.4442 triethylamine and be neutralized reaction, reaction
10min, after adding 32ml deionized water to carry out emulsifying, adds 0.16g ethylenediamine to carry out second chain extending reaction, high-speed stirred is anti-
Answer 20min, reactant mixture is transferred in round-bottomed flask, be that under -0.08mpa, rotary heating, to 55 DEG C, is sloughed in vacuum
Acetone, prepares the biological base water polyurethane that solid content is 30%.
Understand in conjunction with above-described embodiment and Fig. 1, it is raw material that the present invention adopts the lactic acid of bio-based, by polylactic acid multi-element alcohol
With the reaction of isocyanates, hydrophilic chain extender, prepare biological base water polyurethane, preparation method is simple, preparation
Aqueous polyurethane solid content is higher, between 30～60%.
Performance test:
By manufactured in the present embodiment biology base water polyurethane carry out respectively bin stability, filming performance, tensile strength,
The performance test such as light transmittance and biological degradability, and the method for testing of each performance is as follows:
Aqueous polyurethane emulsion bin stability: take certain 1～3ml aqueous polyurethane emulsion in centrifuge tube, be placed in
In few 3000r/min, setting speed is 3000r/min, centrifugation time 15min.Criterion: supernatant liquid is as clear as crystal, under
Layer precipitation is stable, and stability is poor, is designated as c level；Supernatant liquid muddiness is transparent, and there is slight precipitation in lower floor, and stability is slightly good, is designated as b
Level；It is not layered up and down, good stability, be designated as a level.
Filming performance: a, surface drying time, take 2～3ml aqueous polyurethane emulsion, are uniformly distributed in the bopet after corona (double
To drawing refreshing polyethylene terephthalate) surface, using the 10# bar of rds, scratch, be placed in 80 DEG C of electric heating aerators, when
Touch face with finger, feel somewhat tacky, but no emulsion is sticked together on finger, record surface drying time ts, obtain aqueouss and gather
Urethane glued membrane.B, minimum film formation temperature, take appropriate emulsion coating on a metal plate, using minimum film formation temperature analyzer
(rjd451, Shanghai Rong Jida instrument Science and Technology Ltd.), test forms the minimum temperature t of continuously transparent thin filmem.
Tensile strength: take aqueous polyurethane emulsion in each embodiment, make glued membrane in 80 DEG C of aerators, according to gb/
T528-2009 carries out test test to the tensile strength of glued membrane and elongation at break, and test environment is 25 DEG C of room temperature, stretches gauge length
For 25mm, rate of extension is 100mm/min.Result of the test takes the meansigma methodss of 5 samples.
Light transmittance: take aqueous polyurethane emulsion in each embodiment, make glued membrane in 80 DEG C of aerators, take 4cm × 4cm face
Long-pending sample, measures the visible of each embodiment glued membrane using spectrophotometer 722n (Shanghai precision instrumentation company limited system)
Light transmission rate.
Biodegradability: take aqueous polyurethane emulsion in each embodiment, make glued membrane in 80 DEG C of aerators；1st, biological
It is degraded to virgin rubber film quality half required time t1/2, weigh 100m g film forming matter and mix homogeneously with 500g fine particle and soil, be encased in
In wide mouthed bottle, add appropriate distilled water to control mixture humidity, make the environment in wide mouthed bottle be beneficial to microorganism and grow up, setting is empty
White test, that is, same environment is set, and simply blank assay does not add and tests into membrane sample；At regular intervals to film forming matter in soil
Residual qualities are measured, note glued membrane quality degrade the half to input amount when required time be t1/2.2nd, the survey of Anti-mildew capability
Fixed: the growth of microorganism experiment carrying out film forming matter according to astmg21-90, measure the Anti-mildew capability of the film forming matter being obtained, note is mould
The natural law that bacteria growing reaches when 60% is d60.
The property indices of the biological base water polyurethane of embodiment preparation shown in table 1 are obtained
The property indices of the biological base water polyurethane of table 1 embodiment 1～16
Test result can draw as shown in Table 1, the excellent storage stability of the aqueous polyurethane that the present invention provides, film forming table
The dry time is short, and minimum film formation temperature is low, has outstanding tensile strength after film forming, has fabulous biology concurrently as bio-based materials
Degradability, degradation speed is fast, and under the degraded environment of simulation, fungus growth speed is fast.Wherein, embodiment 2,4,6 and 8 provides
More preferably, that is, aqueous polyurethane emulsion is 3000r/min in rotating speed to combination property, is centrifuged 15 minutes, emulsion is not stratified, is becoming simultaneously
During film, surface drying time is less than 35s, not higher than 7 DEG C of minimum film formation temperature, and film forming after-drawing intensity is not less than 10mpa, light transmittance
It is not less than 85%, biodegradation to virgin rubber film quality half required time t1/2Less than 60 days, fungus growth was to more than 60% institute
Take time less than 20 days.Particularly, the aqueous polyurethane emulsion obtained by embodiment 8, is 3000r/min in rotating speed, is centrifuged 15
Minute, emulsion is not stratified, and in film forming, surface drying time is less than 30s simultaneously, not higher than 5 DEG C of minimum film formation temperature, film forming post-tensioning
Stretch intensity and be not less than 15mpa, light transmittance is not less than 86%, biodegradation to virgin rubber film quality half required time t1/2It is less than
32 days, fungus growth to more than 60% required time was less than 15 days, and within the scope of the present invention, combination property is best.Therefore this
The aqueous polyurethane of bright preparation belongs to environment-protecting polyurethane, and the excellent functional improvement application of aqueous polyurethane.
Above example is only optimal and illustrates, and is not the restriction to embodiments of the present invention.Except above-described embodiment
Outward, the present invention also has other embodiment.All employing equivalents or the technical scheme of equivalent transformation formation, all fall within the present invention
The protection domain requiring.
Claims (9)
1. a kind of biology base water polyurethane preparation method it is characterised in that: comprise the following steps:
1) prepare polylactic acid multi-element alcohol: lactic acid, small molecule dihydroxylic alcohols and catalyst a are reacted under inert gas conditions, preparation
Obtain polylactic acid multi-element alcohol；
2) prepare base polyurethane prepolymer for use as: described step 1) the polylactic acid multi-element alcohol prepared is with isocyanates under inert gas conditions
Reaction, is subsequently adding catalyst b and carries out catalytic reaction, prepare base polyurethane prepolymer for use as；
3) prepare biological base water polyurethane: to described step 2) add dihydroxylic alcohols containing hydrophilic group in the base polyurethane prepolymer for use as prepared
Carry out first time chain extending reaction, add triethylamine and be neutralized reaction, after adding deionized water to carry out emulsifying, add chain extender
Carry out second chain extending reaction, prepare biological base water polyurethane.
2. according to claim 1 biology base water polyurethane preparation method it is characterised in that: described small molecule binary
Alcohol is one of propylene glycol, ethylene glycol, bis-phenol a, bis-phenol s, 1,4- butanediol, neopentyl glycol and diglycol.
3. according to claim 1 biology base water polyurethane preparation method it is characterised in that: described catalyst a is
Zinc Isoocatanoate, isooctyl acid bismuth, dibutyl tin laurate, stannous octoate, oxalic acid butyl tin, tetrabutyl titanate and metatitanic acid four are different
In propyl ester one or more.
4. according to claim 1 biology base water polyurethane preparation method it is characterised in that: described catalyst b is
One of stannous octoate, stannous oleate, dibutyltin dilaurate, phenyl mercury propionate and lead octoate or more than one.
5. according to claim 1 biology base water polyurethane preparation method it is characterised in that: described isocyanates are
Methylene diisocyanate, 4,4'- methylene two carbanil, PPDI, tri-methyl hexamethylene two isocyanide
Acid esters, dimethyl diphenyl diisocyanate, O-phthalic group diisocyanate, 2,4 tolylene diisocyanate, naphthalene two Carbimide.
One of ester, isophorone diisocyanate and dicyclohexyl methyl hydride diisocyanate or more than one.
6. according to claim 1 biology base water polyurethane preparation method it is characterised in that: described containing hydrophilic group two
First alcohol is one of dihydromethyl propionic acid, dimethylolpropionic acid or two kinds.
7. according to claim 1 biology base water polyurethane preparation method it is characterised in that: described chain extender be second
In diamidogen, 1,4- butanediol, ethylene glycol, neopentyl glycol, diglycol, trimethylolpropane one or more.
8. according to claim 1 biology base water polyurethane preparation method it is characterised in that: described polylactic acid multi-element
The hydroxyl value of alcohol is 28～224mg koh/g, and acid number is less than or equal to 2mg koh/g.
9. a kind of biology base water polyurethane it is characterised in that: described biology base water polyurethane be according to claim 1～8
The preparation method of the biological base water polyurethane described in middle any one prepares.
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| CN109096466A (en) * | 2018-07-17 | 2018-12-28 | 合肥科天水性科技有限责任公司 | A kind of preparation method of biology base water polyurethane bass |
| CN109295731A (en) * | 2018-09-03 | 2019-02-01 | 金莎 | A kind of biodegradable aqueous polyurethane warp yarn sizing slurry |
| CN110564355A (en) * | 2019-09-23 | 2019-12-13 | 皇冠（太仓）胶粘制品有限公司 | Bio-based polyurethane pressure-sensitive adhesive and preparation method thereof |
| CN112430308A (en) * | 2020-11-24 | 2021-03-02 | 中南大学 | Preparation method of bio-based high-performance waterborne polyurethane resin and product thereof |
| CN114085366A (en) * | 2021-10-22 | 2022-02-25 | 万果新材料科技(上海)有限公司 | Polylactic acid alcohol ester glycol, biodegradable polyurethane hot melt adhesive and preparation method thereof |
| CN115110315A (en) * | 2022-08-03 | 2022-09-27 | 广东德美精细化工集团股份有限公司 | Bio-based water-based blocked isocyanate crosslinking agent and preparation method thereof |
| CN115710339A (en) * | 2022-11-10 | 2023-02-24 | 江苏休伦新材料有限公司 | Bio-based waterborne polyurethane for clothing leather surface layer and preparation method thereof |
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| CN109096466A (en) * | 2018-07-17 | 2018-12-28 | 合肥科天水性科技有限责任公司 | A kind of preparation method of biology base water polyurethane bass |
| CN109295731A (en) * | 2018-09-03 | 2019-02-01 | 金莎 | A kind of biodegradable aqueous polyurethane warp yarn sizing slurry |
| CN110564355A (en) * | 2019-09-23 | 2019-12-13 | 皇冠（太仓）胶粘制品有限公司 | Bio-based polyurethane pressure-sensitive adhesive and preparation method thereof |
| CN112430308A (en) * | 2020-11-24 | 2021-03-02 | 中南大学 | Preparation method of bio-based high-performance waterborne polyurethane resin and product thereof |
| CN112430308B (en) * | 2020-11-24 | 2021-12-21 | 中南大学 | Preparation method of bio-based high-performance waterborne polyurethane resin and product thereof |
| CN114085366A (en) * | 2021-10-22 | 2022-02-25 | 万果新材料科技(上海)有限公司 | Polylactic acid alcohol ester glycol, biodegradable polyurethane hot melt adhesive and preparation method thereof |
| CN115110315A (en) * | 2022-08-03 | 2022-09-27 | 广东德美精细化工集团股份有限公司 | Bio-based water-based blocked isocyanate crosslinking agent and preparation method thereof |
| CN115110315B (en) * | 2022-08-03 | 2023-10-17 | 广东德美精细化工集团股份有限公司 | Bio-based water-based blocked isocyanate crosslinking agent and preparation method thereof |
| CN115710339A (en) * | 2022-11-10 | 2023-02-24 | 江苏休伦新材料有限公司 | Bio-based waterborne polyurethane for clothing leather surface layer and preparation method thereof |
| CN116178662A (en) * | 2023-04-24 | 2023-05-30 | 吉林天泽二氧化碳科技有限公司 | Water-based polythiourethane emulsion and preparation method thereof |
| CN116178662B (en) * | 2023-04-24 | 2023-06-27 | 吉林天泽二氧化碳科技有限公司 | Water-based polythiourethane emulsion and preparation method thereof |
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