CN111454465A - Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof - Google Patents
Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof Download PDFInfo
- Publication number
- CN111454465A CN111454465A CN202010331249.6A CN202010331249A CN111454465A CN 111454465 A CN111454465 A CN 111454465A CN 202010331249 A CN202010331249 A CN 202010331249A CN 111454465 A CN111454465 A CN 111454465A
- Authority
- CN
- China
- Prior art keywords
- modified lignin
- lignin
- dispersant
- component
- polyurethane foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The invention discloses a modified lignin, a full-water-based low-density flame-retardant flexible polyurethane foam composition and a preparation method thereof, wherein the modified lignin is prepared by the following method: uniformly mixing oligomer diol and dipropylene glycol, adding neopentyl glycol to completely dissolve, adding lignin, castor oil polyoxyethylene ether and a composite dispersant under stirring, and carrying out microwave reaction in a microwave reactor at 200-250W and 150 +/-5 ℃ for 5 min; the composite dispersant comprises a dispersant 1 and a dispersant 2; wherein the dispersant 1 is at least one of BYK-W961, BYK-W966, BYK-W969, BYK-9076, BYK-9077 and the like; the dispersant 2 is at least one of anilinopropyltriethoxysilane, anilinopropyltrimethoxysilane, anilinopropyldimethoxysilane, and the like. The full-water-based low-density flame-retardant flexible polyurethane foam composition comprises a component A, a component B and a component C, wherein the component A comprises modified lignin, polyether polyol, polymer polyol, a flame retardant, water, a reactive catalyst and a foam stabilizer; the component B is isocyanate containing modified lignin.
Description
Technical Field
The invention belongs to the field of polyurethane, and particularly relates to improvement of bi-component full-water-based low-density flame-retardant flexible polyurethane foam.
Technical Field
1. Full water-based low-density soft polyurethane spraying foam prior art
Compared with the traditional hard foam material, the full water-based low-density soft polyurethane spraying system has more outstanding advantages: comprises (1) foaming with water, and zero ODP, and meets the requirement of environmental protection; (2) the foam density is low, the weight is light, the energy is saved, and the cost is saved; (3) the open-cell foam has good moisture resistance and mildew resistance; (4) the flame retardant property is good, and the requirements of industrial indexes such as buildings, automobiles and the like can be met; (5) high production efficiency and the like. Based on the advantages, the full water-based low-density soft polyurethane spray foam can be used as an inner wall heat-insulating and sound-absorbing material in automobile interior and buildings, and can be used as a precision instrument packaging material, a filling material and the like in transportation.
Patent document CN 102942676 a relates to a full water-based low-density soft polyurethane spray type composite polyether and a preparation method thereof; CN 108148168A relates to flame-retardant combined polyether polyol and polyurethane foam for a passenger car ceiling and a preparation method thereof; CN106589277A relates to an ultra-low density all-water based polyurethane foam for packaging materials; CN105859998A relates to a composition for foaming low-density full water polyurethane, which can be used for filling heat preservation, heat insulation, sound insulation and moisture prevention of buildings and can also be used for packaging precise instruments. With the gradually increasing requirements of downstream customers on mechanical properties, heat resistance, flame retardancy and the like of materials, the prior art cannot meet the use requirements. Meanwhile, all the raw materials used by the technology are derived from fossil raw materials and have no regeneration.
2. Prior art for the use of lignin in polyurethane materials
Lignin is the second most abundant natural polymer next to the cellulose inventory, widely present in the natural woody tissue, and is an important component constituting plant cell walls, mainly hardening the cell walls by forming a cross-woven network. The lignin is formed by three different phenylpropane structural units of hydroxyphenyl (H), guaiacyl (G) and syringyl (S), which are connected with each other in a three-dimensional network structure, the molecules are mainly connected by carbon-carbon bonds and ether bonds, and the molecular chain contains abundant active groups such as hydroxyl, carboxyl, carbonyl and the like, so that the application of the lignin in high polymer materials becomes possible.
The method is simple, convenient and easy to implement, has low cost, but has the problems of poor compatibility with a system, unobvious modification effect and the like; the other method is that the content of specific functional groups is increased by chemical modification, such as hydroxylation, amination, oxypropylation, esterification and the like, the reactivity of the functional groups in lignin can be improved by modification, the modified lignin can be used as an active hydroxyl component of polyurethane to participate in polymerization reaction, and is directly connected with a matrix material through a chemical bond, so that the compatibility and the stability are better, but the increase of the process also brings the increase of the cost, and other components introduced during modification can also have adverse effects on the environmental protection performance of the system.
Patent document CN 108559046 a relates to an ozonized modified lignin polyurethane and a preparation method thereof, wherein the ozonized modified lignin polyurethane has excellent mechanical properties and adhesion, and can reduce the production cost of polyurethane, and the obtained polyurethane can be used in the fields of films, coatings, adhesives and the like. Ozonization modification is carried out on lignin to obtain ozonized modified lignin, then the ozonized modified lignin is polymerized with raw materials such as isocyanate, polyol, catalyst and the like according to a certain proportion to prepare ozonized modified lignin polyurethane oligomer, and then the ozonized modified lignin polyurethane oligomer is obtained by thermal curing molding. This technique is not suitable for two-component spray polyurethane foam systems.
Patent document CN104744659A provides a biomass polyol composition and a biomass polyurethane foam material. Lignin is uniformly dispersed in the polyol by a modifier and a grinding dispersion process to obtain the biomass polyol composition. And the biomass polyol composition is used for preparing the biomass polyurethane foaming material with high lignin content, high compressive strength and excellent flame resistance. The molecular weight of dihydric alcohol, trihydric alcohol, tetrahydric alcohol and the mixture thereof adopted by the technology is less than 500, the produced polyurethane foam is rigid foam, the foaming ratio is below 10, and the lightweight requirement of the application field is not met.
Patent document CN109486382A discloses a novel lignin-based polyurea coating and a preparation method thereof. According to the technology, lignin is aminated and then used for the polyurea coating, and the obtained coating shows better ultraviolet aging resistance, thermal stability, acetone resistance and salt resistance. However, the amination process is a mannich reaction, formaldehyde is used as an intermediate, and incomplete removal of residual formaldehyde can greatly increase the formaldehyde volatilization amount of the material, so that the emission performance of the product is unqualified.
Patent document CN1651478A discloses a method for preparing high-boiling alcohol lignin polyurethane with high purity, low ash content and good chemical activity. Dissolving a certain amount of high-boiling alcohol lignin or a high-boiling alcohol lignin derivative in an organic solvent, mixing the solution with polyol or a solution of polyol, heating or stirring the mixture to be completely and uniformly mixed, then adding a certain amount of isocyanate, heating the mixture to react, introducing the lignin into polyurethane by the method and obtaining better activity, but the organic solvent used in the formula of the method has great influence on the mechanical property and the environmental protection property of the material.
Patent document CN105637036A uses dry lignin reacted with isocyanate and as active NCO component reacted with polyol for the production of polyurethane products. However, the modified isocyanate prepared by the technology has high viscosity, and additives such as a foaming agent, a flame retardant and the like are required to be added for adjustment, so that the reaction ratio and the environmental protection property are influenced; the reaction activity of the technology can not meet the requirement of full water spray foam on gel time, and the density of the prepared foam material is more than 20kg/m3This is not favorable to the light weight of the product.
The prior art has the following defects:
(1) with the continuous improvement of application requirements, the mechanical property, heat resistance and flame retardance of the spraying foam material in the prior art can not meet the requirements, the properties can be improved by adding lignin, but the problems of poor compatibility, unobvious property improvement and the like exist when the lignin is directly added;
(2) in the lignin modification scheme in the prior art, a volatile organic solvent is generally used, or formaldehyde is used as an intermediate, which is unfavorable for the environmental protection of the material, so that indexes such as TVOC, atomization, formaldehyde volatilization and odor of the material exceed standards;
(3) in the lignin modification scheme in the prior art, polyol with the molecular weight of below 500 is generally used, so that the flexibility of foam is influenced, and the prepared material is brittle;
(4) the viscosity and activity of lignin modified isocyanate in the prior art cannot meet the use requirements of low-density spray foam;
(5) the problems of agglomeration, sedimentation and the like are easy to occur under the condition that the content of the lignin exceeds 20 percent.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide modified lignin, wherein the modified lignin is used in a polyurethane soft foam formula and does not settle, and the prepared polyurethane foam material has higher flame retardant property, environmental protection property and thermal stability.
The second technical problem to be solved by the invention is to provide a full water-based low-density flame-retardant flexible polyurethane foam composition prepared by using the modified lignin.
The third technical problem to be solved by the invention is to provide a preparation method of the full water-based low-density flame-retardant flexible polyurethane foam composition.
In order to solve the first technical problem, the invention provides a preparation method of modified lignin, which comprises the following steps: uniformly mixing 50-60 parts of oligomer diol and 40-50 parts of dipropylene glycol, adding 20-25 parts of neopentyl glycol at 60-70 ℃ to completely dissolve the neopentyl glycol, cooling to room temperature, adding 100 parts of lignin, 1-3 parts of castor oil polyoxyethylene ether and 1 part of composite dispersant under stirring, then putting into a microwave reactor, and carrying out 5min at 150 +/-5 ℃ under 200-250W to obtain the modified lignin. The oligomer diol is preferably a polypropylene glycol having a molecular weight of 600, 800 or 1000; the composite dispersant comprises a dispersant 1 and a dispersant 2; wherein the dispersant 1 comprises at least one of BYK-W961, BYK-W966, BYK-W969, BYK-9076 or BYK-9077 and the like which are products of Bike auxiliary (Shanghai) Limited company; the dispersant 2 comprises at least one of aniline propyl triethoxysilane, aniline propyl trimethoxysilane or aniline propyl dimethoxysilane; the mass ratio of the dispersing agent 1 to the dispersing agent 2 is preferably 1: 1-1: 3. The lignin is one or more of alkali lignin, sulfate lignin and the like.
In order to solve the second technical problem, the invention provides a full water-based low-density flame-retardant flexible polyurethane foam composition, wherein the component A comprises the modified lignin, polyether polyol, polymer polyol, a flame retardant, water, a reactive catalyst and a foam stabilizer; the component B is isocyanate containing the modified lignin.
Further, the all-water-based low-density flame-retardant flexible polyurethane foam composition comprises the following components in parts by mass: 10-35% of modified lignin, 20-30% of polyether polyol, 1-15% of polymer polyol, 10-20% of flame retardant, 10-25% of water, 0.1-5% of reactive catalyst, preferably 1-3% of reactive catalyst and 0.01-1.5% of foam stabilizer.
The polyether polyol is preferably one or more of ethylene oxide-propylene oxide copolyether triols with primary hydroxyl content of more than 50% and number average molecular weight of 3000-6500.
The polymer polyol is preferably one or more of styrene-acrylonitrile graft polymer polyols based on ethylene oxide-propylene oxide copolyether triol, and the hydroxyl value is 18-35 mgKOH/g.
The flame retardant is preferably one or more of TCEP, TCPP, TDCP, melamine phosphate, dimethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, Exolit OP550 or Exolit OP560 (product of Laine, Switzerland) and the like, and is not exhaustive.
The reaction type catalyst is preferably one or more of Dimethylethanolamine (DMEA), Dimethylaminoethoxyethanol (DMAEE), trimethylhydroxyethylpropylenediamine, N, N, N ' -trimethyl-N ' -hydroxyethylbisaminoethyl ether, Tetramethyldipropylenetriamine (TMBPA), N-methyl N ' -hydroxyethylpiperazine or the like.
The foam stabilizer is preferably one or more of products L-580, L-580 AP, L-580K, L-3001, L-3002 or L-3620 from Myzus Corp.
The component B comprises the following components in percentage by mass:
2.5-5% of modified lignin, 2.5-5% of dihydric alcohol modifier, 40-45% of 4, 4' -MDI and 50% of polymeric MDI. The diol modifier is preferably one or more of polypropylene glycol, polytetrahydrofuran glycol or polycaprolactone glycol with molecular weight of 1000, 2000 and 4000, and the like.
The polymeric MDI preferably comprises one or more of Bayer 44V 20L, Tantawawa PM200, Huntsman 5005, BASF M20S, and the like.
The composition of the invention can be used for producing low-density low-emission all-water-based flexible polyurethane foam by reacting A, B components in a volume ratio of 1: 1 through a spraying process. The invention partially replaces polyether polyol from fossil sources with renewable bio-based raw materials, and conforms to the strategy of environmental protection and sustainable development.
In order to solve the third technical problem, the invention provides a preparation method of a full water-based low-density flame-retardant flexible polyurethane foam composition, which comprises the following steps:
preparation of a component A: and (2) uniformly stirring and mixing polyether polyol, polymer polyol, a flame retardant, a reactive catalyst and a foam stabilizer at 25-40 ℃, then adding water and modified lignin while stirring, and uniformly mixing.
B, preparation of a component:
(1) and (3) vacuumizing, drying and dehydrating the modified lignin.
(2) Adding the dehydrated modified lignin, the dihydric alcohol modifier and 4, 4' -MDI into a reaction vessel, adding 0.01-0.05% of stannous octoate, and stirring and reacting at 80-85 ℃ for 120 min.
(3) Adding polymeric MDI, and stirring for 30min at 30-40 ℃ to finish the process.
The present invention has the following advantageous effects
(1) The lignin is modified, so that the application of the bio-based renewable resources in the full-water-based low-density soft polyurethane spray foam is realized, and the use content is higher.
(2) The dissolving ratio of the lignin is improved by adopting a synergistic co-dissolving mode, and the prepared modified lignin has no adverse effect on the flexibility of the foam.
(3) The modified lignin prepared by the method does not contain volatile organic solvents, does not use intermediates such as formaldehyde and the like, and is environment-friendly.
(4) The modified lignin prepared by the invention can not cause collapse and shrinkage of polyurethane foam.
(5) The composition A, B has the components of modified lignin introduced simultaneously, so that a higher lignin addition proportion is obtained under the condition of keeping a faster reaction rate and a higher foaming ratio, the modified lignin has good compatibility with a system, and no layered settlement exists, thereby improving the heat resistance, the pressure resistance and the flame retardance. The two groups of components have high reactivity and can complete foaming and gelling within 10s, and the foaming ratio is high, and the density is less than 20kg/m3。
(6) The lignin is introduced into the polyurethane by physical and chemical methods, so that the mechanical property, the thermal stability, the ageing resistance, the hydrophobicity, the flame retardance, the biodegradability and other properties of the polyurethane material are improved, and in addition, the proper introduction of the lignin to modify the polyurethane can reduce the material cost, reduce the consumption of fossil resources, regenerate the raw material sources and protect the ecological environment.
Detailed Description
The invention is further illustrated by the following specific examples, wherein the parts are by weight.
Example 1
The preparation of the modified lignin comprises the steps of uniformly mixing 50 parts of polypropylene glycol (molecular weight 600) and 50 parts of dipropylene glycol, adding 20 parts of neopentyl glycol at 65 ℃ to completely dissolve the neopentyl glycol, slowly cooling to room temperature, adding 100 parts of alkali lignin, 2 parts of castor oil polyoxyethylene ether (Haian petrochemical company E L-40), BYK-W9610.2 parts of aniline propyl dimethoxysilane and 0.4 part of aniline propyl dimethoxysilane while stirring, then placing the mixture into a microwave reactor, and treating the mixture at 220W and 150 +/-5 ℃ for 5min to obtain the modified lignin.
Preparation of polyurethane composition a component: firstly, adding polyether polyol, polymer polyol, a flame retardant, a reactive catalyst and a foam stabilizer, and stirring for 15min at 35-40 ℃; then adding water and modified lignin while stirring, stirring for 60min at 35-40 ℃, and discharging.
The component A comprises 20 parts of EP-330N (a product of Lanxingdong Dayu, the hydroxyl value is 32.5-35.5 mgKOH/g), 3.5 parts of POP31/28 (a product of Lanxingdong Dayu, the hydroxyl value is 26-29 mgKOH/g), 30 parts of modified lignin, 18 parts of TCPP, 25 parts of water, 1 part of dimethylaminoethoxyethanol, 2 parts of N-methyl N' -hydroxyethyl piperazine and 0.5 part of L-580K.
Preparation of polyurethane composition B component: firstly, stirring and dehydrating the modified lignin for 2 hours at the temperature of 100-105 ℃ and the relative vacuum degree of-0.09 to-0.085 MPa, and cooling to room temperature. And then adding the dehydrated modified lignin, the glycol modifier and the diphenylmethane diisocyanate into a reaction container, adding 0.02% of stannous octoate, and stirring and reacting at 82-85 ℃ for 120 min.
The component B comprises 5 parts of modified lignin, 5 parts of polypropylene glycol (molecular weight 2000), 40 parts of 4, 4' -MDI and 50 parts of 44V 20L 50 from Bayer company.
Foam swatches were prepared and tested for performance using the composition A, B components reacted on a spray coater at 55 c and 1200 psi.
Example 2
The preparation of the modified lignin comprises the steps of uniformly mixing 60 parts of polypropylene glycol (with the molecular weight of 800) and 40 parts of dipropylene glycol, adding 22 parts of neopentyl glycol at the temperature of 60 ℃ to completely dissolve the neopentyl glycol, cooling to room temperature, adding 100 parts of sulfated lignin, L-403 parts of castor oil polyoxyethylene ether, BYK-90770.2 parts of aniline propyl triethoxysilane and 0.3 part of aniline propyl triethoxysilane while stirring, then placing the mixture into a microwave reactor, and treating the mixture at the temperature of 150 +/-5 ℃ for 5min at 225W to obtain the modified lignin.
Preparation of polyurethane composition a component: firstly, adding polyether polyol, polymer polyol, a flame retardant, a reactive catalyst and a foam stabilizer, and stirring for 15min at 35-40 ℃; then adding water and modified lignin while stirring, stirring for 60min at 35-40 ℃, and discharging.
The component A comprises 28 parts of EP-3600 (a product of Lanxindong Dayu company, the hydroxyl value is 26-30 mgKOH/g), 10 parts of POP43 (a product of Lanxindong Dayu company, the hydroxyl value is 29-33 mgKOH/g), 19.2 parts of modified lignin, 10 parts of Exolit OP 55010 parts, 10 parts of melamine, 20 parts of water, 1.2 parts of dimethylaminoethoxyethanol, 1.3 parts of trimethylhydroxyethyl propylene diamine and L-30020.3 parts.
Preparation of polyurethane composition B component: firstly, stirring and dehydrating the modified lignin for 2 hours at the temperature of 100-105 ℃ and the relative vacuum degree of-0.09 to-0.085 MPa, and cooling to room temperature. And then adding the dehydrated modified lignin, the glycol modifier and the diphenylmethane diisocyanate into a reaction container, adding 0.03% of stannous octoate, and stirring and reacting at 80-83 ℃ for 120 min.
The component B comprises the following components: 5 parts of modified lignin, 3 parts of polytetrahydrofuran diol (molecular weight 1000), 42 parts of 4, 4' -MDI, PM200 of Wanhua company: 50 parts of the raw materials.
Foam swatches were prepared and tested for performance using the composition A, B components reacted on a spray coater at 55 c and 1200 psi.
Comparative example 1
The component A comprises: the modified lignin was replaced by polyether polyol EP-330N and the rest of the formulation was the same as in example 1.
Component B A Bayer 44V 20L was used.
Comparative example 2
The component A comprises: the modified lignin was replaced by unmodified alkali lignin and the rest of the formulation was the same as in example 1.
Component B A Bayer 44V 20L was used.
In the above examples, A, B component composition was used to prepare foam blocks by reaction on a spray coater at 55 ℃ and 1100-1200 psi, and the performance was tested.
TABLE 1 comparison of feed liquid properties of component A of examples and comparative examples
TABLE 2 comparison of foaming parameters and foam Properties of the examples and comparative examples
Claims (10)
1. A modified lignin is characterized by being prepared by the following steps: uniformly mixing 50-60 parts of oligomer glycol and 40-50 parts of dipropylene glycol, adding 20-25 parts of neopentyl glycol at 60-70 ℃ to completely dissolve the neopentyl glycol, cooling to room temperature, adding 100 parts of lignin, 1-3 parts of castor oil polyoxyethylene ether and 1 part of composite dispersant under the condition of stirring, then putting into a microwave reactor, and obtaining modified lignin at the temperature of 150 +/-5 ℃ for 5min under 200-250W; the oligomer diol refers to polypropylene glycol with molecular weight of 600, 800 or 1000; the composite dispersant comprises a dispersant 1 and a dispersant 2; wherein the dispersant 1 is at least one of BYK-W961, BYK-W966, BYK-W969, BYK-9076 or BYK-9077 products of Bike auxiliary agent (Shanghai); the dispersant 2 is at least one of aniline propyl triethoxysilane, aniline propyl trimethoxysilane or aniline propyl dimethoxysilane.
2. The modified lignin according to claim 1, wherein the mass ratio of the dispersant 1 to the dispersant 2 is 1: 1 to 1: 3.
3. The modified lignin according to claim 1, wherein the lignin is one or more of an alkali lignin or a kraft lignin.
4. An all-water based low density flame retardant flexible polyurethane foam composition, the component A comprising the modified lignin of claim 1, a polyether polyol, a polymer polyol, a flame retardant, water, a reactive catalyst, a foam stabilizer; the component B is isocyanate containing the modified lignin of claim 1.
5. The all-water-based low-density flame-retardant flexible polyurethane foam composition according to claim 4, wherein the component A comprises the following components in parts by mass: 10 to 35 percent of modified lignin, 20 to 30 percent of polyether polyol, 1 to 15 percent of polymer polyol, 10 to 20 percent of flame retardant, 10 to 25 percent of water, 0.1 to 5 percent of reactive catalyst and 0.01 to 1.5 percent of foam stabilizer; the component B comprises the following components in percentage by mass: 2.5 to 5 percent of modified lignin, 2.5 to 5 percent of dihydric alcohol, 40 to 45 percent of 4, 4' -MDI and 50 percent of polymeric MDI.
6. The flexible polyurethane foam composition as claimed in claim 4, wherein the polyether polyol is one or more of ethylene oxide-propylene oxide copolyether triols having a primary hydroxyl group content of > 50% and a number average molecular weight of 3000-6500, the polymer polyol is one or more of styrene-acrylonitrile graft polymer polyols based on ethylene oxide-propylene oxide copolyether triols and having a hydroxyl value of 18-35 mgKOH/g, the flame retardant is one or more of TCEP, TCPP, TDCP, melamine phosphate, dimethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, Exolit OP550 products of Switzerland Exolit OP560 products of Switzerland, the reaction type catalyst is one or more of Dimethylethanolamine (DMEA), Dimethylaminoethoxyethanol (DMAEE), trimethylhydroxyethylpropylene diamine, N, N ' -trimethyl-N ' -hydroxyethylbisaminoethyl ether, tetramethyldipropylenetriamine (BPA) or N-methylethyl-N ' -hydroxyethyl piperazine stabilizer, one or more of foam stabilizers 30036, 36580, L-36580 or 36580.
7. The all-water based low density flame retardant flexible polyurethane foam composition according to claim 4, wherein said polymeric MDI is one or more of Bayer 44V 20L, Tantawawa PM200, U.S. Huntsman 5005, BASF M20S.
8. The flexible polyurethane foam composition of claim 5, wherein the diol is one or more of polypropylene glycol, polytetrahydrofuran glycol or polycaprolactone glycol with molecular weight of 1000, 2000, 4000.
9. The all-water based low-density flame-retardant flexible polyurethane foam composition as claimed in claim 4, wherein the components are reacted in a volume ratio of 1: 1 by spray process A, B to produce a low-density low-emission all-water based flexible polyurethane foam.
10. A process for preparing a fully water based, low density, flame retarded, flexible polyurethane foam composition according to any one of claims 4 to 9 comprising the steps of:
preparation of a component A: stirring and uniformly mixing polyether polyol, polymer polyol, a flame retardant, a reactive catalyst and a foam stabilizer at 25-40 ℃, then adding water and modified lignin while stirring, and uniformly mixing;
b, preparation of a component:
(1) vacuumizing, drying and dehydrating the modified lignin;
(2) adding the dehydrated modified lignin, dihydric alcohol and 4, 4' -MDI into a reaction container, adding 0.01-0.05% of stannous octoate, and stirring and reacting at 80-85 ℃ for 120 min;
(3) adding polymeric MDI, and stirring for 30min at 30-40 ℃ to finish the process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010331249.6A CN111454465B (en) | 2020-04-15 | 2020-04-15 | Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010331249.6A CN111454465B (en) | 2020-04-15 | 2020-04-15 | Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111454465A true CN111454465A (en) | 2020-07-28 |
| CN111454465B CN111454465B (en) | 2022-05-24 |
Family
ID=71674680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010331249.6A Active CN111454465B (en) | 2020-04-15 | 2020-04-15 | Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111454465B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115141337A (en) * | 2021-03-29 | 2022-10-04 | 万华化学集团股份有限公司 | Micro-foaming polyurethane damping material and preparation method thereof |
| CN116023614A (en) * | 2022-09-16 | 2023-04-28 | 江苏米尔化工科技有限公司 | High-fluidity flame-retardant polyurethane soft foam composition |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2052487A1 (en) * | 1990-10-13 | 1992-04-14 | Shigeo Hirose | Polyurethane and method of preparing the same |
| CN1176643A (en) * | 1995-12-29 | 1998-03-18 | K·R·库泼 | Lignin based polyols |
| JP2003313266A (en) * | 2002-04-19 | 2003-11-06 | Fukuvi Chem Ind Co Ltd | Method for producing biodegradable soft polyurethane foam |
| CN102675582A (en) * | 2012-05-17 | 2012-09-19 | 西南科技大学 | Preparation method of polyurethane foam materials based on liquefied lignin calcium sulfonate polyalcohol |
| CN103289056A (en) * | 2013-07-07 | 2013-09-11 | 华东理工大学 | Method for producing high-hydroscopicity soft polyurethane foam through bamboo fiber polyhydric alcohol |
| WO2014044234A1 (en) * | 2012-09-21 | 2014-03-27 | SYNPO, akciová společnost | A method of preparation of polyurethane materials containing lignin, a polyurethane material prepared according to this method |
| CN104411772A (en) * | 2012-06-01 | 2015-03-11 | 斯托拉恩索公司 | A composition in the form of a dispersion comprising a lignin, a method for the manufacturing thereof and use thereof |
| CN104744659A (en) * | 2013-12-27 | 2015-07-01 | 财团法人工业技术研究院 | Biomass polyol composition and biomass polyurethane foaming material |
| CN105669935A (en) * | 2016-03-03 | 2016-06-15 | 上海大学 | Hemp stalk core powder modified antibacterial type soft polyurethane composite foaming material |
| CN105916915A (en) * | 2013-12-05 | 2016-08-31 | 斯道拉恩索公司 | A composition in the form of a lignin polyol, a method for the production thereof and use thereof |
| CN107001565A (en) * | 2014-11-25 | 2017-08-01 | Cj第制糖株式会社 | Hard polyurethane foams and preparation method thereof |
| KR20180037927A (en) * | 2018-01-24 | 2018-04-13 | 주식회사 비엠산업 | Instant foam polyurethane packing cushioning material |
| CN109575351A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of lignin-base polyurethane foam and preparation method thereof |
-
2020
- 2020-04-15 CN CN202010331249.6A patent/CN111454465B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2052487A1 (en) * | 1990-10-13 | 1992-04-14 | Shigeo Hirose | Polyurethane and method of preparing the same |
| CN1176643A (en) * | 1995-12-29 | 1998-03-18 | K·R·库泼 | Lignin based polyols |
| JP2003313266A (en) * | 2002-04-19 | 2003-11-06 | Fukuvi Chem Ind Co Ltd | Method for producing biodegradable soft polyurethane foam |
| CN102675582A (en) * | 2012-05-17 | 2012-09-19 | 西南科技大学 | Preparation method of polyurethane foam materials based on liquefied lignin calcium sulfonate polyalcohol |
| CN104411772A (en) * | 2012-06-01 | 2015-03-11 | 斯托拉恩索公司 | A composition in the form of a dispersion comprising a lignin, a method for the manufacturing thereof and use thereof |
| WO2014044234A1 (en) * | 2012-09-21 | 2014-03-27 | SYNPO, akciová společnost | A method of preparation of polyurethane materials containing lignin, a polyurethane material prepared according to this method |
| CN103289056A (en) * | 2013-07-07 | 2013-09-11 | 华东理工大学 | Method for producing high-hydroscopicity soft polyurethane foam through bamboo fiber polyhydric alcohol |
| CN105916915A (en) * | 2013-12-05 | 2016-08-31 | 斯道拉恩索公司 | A composition in the form of a lignin polyol, a method for the production thereof and use thereof |
| CN104744659A (en) * | 2013-12-27 | 2015-07-01 | 财团法人工业技术研究院 | Biomass polyol composition and biomass polyurethane foaming material |
| CN107001565A (en) * | 2014-11-25 | 2017-08-01 | Cj第制糖株式会社 | Hard polyurethane foams and preparation method thereof |
| CN105669935A (en) * | 2016-03-03 | 2016-06-15 | 上海大学 | Hemp stalk core powder modified antibacterial type soft polyurethane composite foaming material |
| CN109575351A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of lignin-base polyurethane foam and preparation method thereof |
| KR20180037927A (en) * | 2018-01-24 | 2018-04-13 | 주식회사 비엠산업 | Instant foam polyurethane packing cushioning material |
Non-Patent Citations (5)
| Title |
|---|
| PATRIZIA CINELLI等: "Green synthesis of flexible polyurethane foams from liquefied", 《EUROPEAN POLYMER JOURNAL》 * |
| SANDRA GÓMEZ FERNÁNDEZ等: "Properties of flexible polyurethane foams containing isocyanate functionalized kraft lignin", 《INDUSTRIAL CROPS AND PRODUCTS》 * |
| 周大纲主编: "《土工合成材料制造技术及性能》", 30 April 2019, 中国轻工业出版社 * |
| 王圣谕: "木质素基聚氨酯弹性材料的制备及其结构与性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
| 薛永兵主编: "《能源与化学工程专业实验指导书》", 31 August 2017, 科学技术文献出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115141337A (en) * | 2021-03-29 | 2022-10-04 | 万华化学集团股份有限公司 | Micro-foaming polyurethane damping material and preparation method thereof |
| CN115141337B (en) * | 2021-03-29 | 2023-08-11 | 万华化学集团股份有限公司 | Micro-foaming polyurethane damping material and preparation method thereof |
| CN116023614A (en) * | 2022-09-16 | 2023-04-28 | 江苏米尔化工科技有限公司 | High-fluidity flame-retardant polyurethane soft foam composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111454465B (en) | 2022-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3033394B1 (en) | Process for the preparation of lignin based polyurethane products | |
| CN101519485B (en) | Wide temperature domain damping polyurethane micropore elastomer material and preparation method thereof | |
| EP2430061B1 (en) | Silicone surfactant for use in polyurethane foams prepared using vegetable oil based polyols | |
| CN111454465B (en) | Modified lignin, full-water-based low-density flame-retardant flexible polyurethane foam composition and preparation method thereof | |
| CN103910850B (en) | A kind of fire-retardant enhancing hard polyurethane foam of phosphatization lignin-base and preparation method thereof | |
| CN111560108A (en) | Full-water polyurethane rigid foam and preparation method and application thereof | |
| CN102827340A (en) | Organosilicon-modified waterborne polyurethane composite material and applications thereof | |
| CN113956777B (en) | Preparation and application methods of self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating | |
| WO2023051435A1 (en) | Halogenated polyphosphate polyol and prepolymer and preparation method therefor, as well as polyurea elastomer composition and polyurea elastomer and application | |
| CN109929087B (en) | Polyurethane rigid foam and preparation method thereof | |
| JP2021161349A (en) | Urethane resin composition and method for producing the same | |
| KR20220099982A (en) | Imide-containing polyester polyols and expanded rigid foams | |
| CN116143983A (en) | Bio-based environment-friendly polyurethane foam material and processing method thereof | |
| KR101634309B1 (en) | Rigid polyurethane spray foam composition of low density | |
| CN116396458A (en) | High-strength, fireproof and anti-dripping lignin-based polyurethane foam and preparation method thereof | |
| CN113321849B (en) | Efficient synergistic flame retardant and preparation method and application thereof | |
| KR20190057038A (en) | Composition for forming eco-friendly polyurethane foam with improved air permeability and antioxidant properties and method for preparing the polyurethane foam | |
| CN114478989B (en) | Flame-retardant polyurethane and preparation method thereof | |
| CN112266463B (en) | Flame-retardant lignin-based rigid polyurethane foam for automotive interior and preparation method thereof | |
| CN115160527A (en) | Preparation method of flame-retardant polyurethane foam containing guanidium phosphate polyether | |
| CN115595057A (en) | Anti-aging single-component polyurethane waterproof coating | |
| KR20190137431A (en) | Polyol composition for forming polyurethane foam and method for preparing the polyurethane foam | |
| CN110003419B (en) | Pre-gel and preparation method and application thereof | |
| CN115246917A (en) | All-water polyurethane rigid foam with anti-crisp property and preparation method and application thereof | |
| CN111454417A (en) | Full-water flame-retardant modified spraying polyurethane foam and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |