CN107417885A - Biomass-based flame-retardant polyurethane flexible sponge foam and preparation method thereof - Google Patents
Biomass-based flame-retardant polyurethane flexible sponge foam and preparation method thereof Download PDFInfo
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- CN107417885A CN107417885A CN201710753052.XA CN201710753052A CN107417885A CN 107417885 A CN107417885 A CN 107417885A CN 201710753052 A CN201710753052 A CN 201710753052A CN 107417885 A CN107417885 A CN 107417885A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/48—Polyethers
-
- 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
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- C08G2110/0008—Foam properties flexible
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of biomass-based flame-retardant polyurethane flexible sponge foam and preparation method thereof, it is characterized in that：By with (a）Fire-retardant modified epoxy soybean oil polyol, (b) polymer polyatomic alcohol are primary raw material, in response type or the catalyst of low smell, physically and/or chemically foaming agent, under foam stabiliser or fire retardant effect, the environmentally friendly renewable biomass flame-retardant polyurethane flexible sponge foam of generation is polymerize with (c) isocyanate component mixed foaming.The biomass-based flame-retardant polyurethane flexible sponge foam of the present invention is produced by using renewable biomass raw material, is reduced foam synthetic products to the dependency degree of oil coal resources, is stabilized product price, also reach the purpose of environmentally friendly low-carbon.
Description
Technical field
The present invention relates to a kind of polyurethane flexible sponge foam and preparation method thereof.
Background technology
The referred to as soft bubble of polyurethane soft foamed plastics, is commonly called as sponge, refers to the flexibility polyurethane foam with certain elasticity
Foam plastics, it is mainly used in furniture mat material, vehicle seat cushion material and various soft liner laminar composites.
The composition that the raw material of the polyurethane flexible sponge foam of prior art is main obtains through refining product for oil, is non-renewable
Resource, it is processed, and process is complicated, and cost is high and pollutes environment.As oil reserve is constantly reduced, International Petroleum Price and
Petrochemical industry class product climbs up and up, the polyalcohol produced with renewable resources such as reproducible biomass-based and recovery vegetable oil
Polyurethane flexible foam as raw material production has wide market development prospect.Biobased polyether polyol be soybean oil,
Rapeseed oil, cottonseed oil or palm oil are the polyol compound of initiation material synthesis, are kind of an environmentally friendly, reproducible resources, and
And have been realized in industrialized production.
At present, biobased polyether polyol is mainly used in the general sponge of no flame-retardancy requirements, and general sponge is one
Kind combustible material, but flame-retardancy requirements, such as perambulator, household articles and interior decoration etc. are also had when some fields are applied.
Therefore, it is necessary to further improve the fire resistance of the soft sponge foam of bio-based polyurethane.
At present, because biobased polyether polyol there are problems that in building-up process, most uses are more to polyethers
In first less demanding hard polyurethane foam of alcohol, used by the collaboration of each polyethers in formula, reach the property required for foam
Energy.
A kind of methods that RPUF is prepared using soybean oil of application number 200810132276.X, including such as
Lower step：1) epoxidation reaction：Soybean oil and epoxidizing agent are reacted, generate epoxidized soybean oil；2) ring-opening reaction：By the ring
Epoxy bond ring-opening reaction, generation mixing hydroxyl fat occur with the nucleopilic reagent containing active hydrogen in the presence of a catalyst for oxygen soybean oil
Fatty acid glyceride；3) alcoholysis reaction and esterification：Add alcohol and heat up and carry out alcoholysis reaction, generation mixing hydroxy fatty acid list
Ester, i.e. soybean oil base polyol；Esterification is carried out using soybean oil base polyol and organic acid and acid anhydrides, generates polyester polyols
Alcohol；4) 100 parts of weight soybean oil base polyols are taken, are sequentially added 80-150 parts weight isocyanate, the ethanol of 0.3-4 parts weight three
After amine, 0.5-4 part weight foam stabilizers are stirred vigorously mixing, 0.5-3 part weight distilled water is added, high-speed stirred is uniformly sent out afterwards
Bubble, is made RPUF.The method mainly prepares epoxidized soybean oil polyester and hard polyurethane foams, and is closed
Into foam do not require fire-retardant.
Application of the application number 201210176034.7 the invention discloses soybean oil polyol in the soft foam materials of PU are prepared.
A kind of soft foam materials of PU, it is made up of following raw material：One kind, soybean oil in TDI, PPG and PEPA is more
First alcohol, the foaming agent of 3-5 mass parts, the foam stabilizer of 0.9-1.5 mass parts, the amines catalyst of 0.2-0.5 mass parts, 0.2-
The tin catalyst of 0.3 mass parts, the crosslinking agent of 1-2 mass parts, wherein, TDI indexes are 1.05；PPG or polyester are more
A kind of gross mass of and soybean oil polyol in first alcohol is 100 mass parts, wherein, soybean oil polyol in gross mass
Percentage is 10-90%.The present invention substitutes Aethoxy Sklerol or polyester alcohol using soybean oil polyol part, can to synthesize poly- ammonia
Ester industry reduces the dependency degree to oil coal resources, while obtained final products are environmentally friendly.The method mainly uses
Soybean oil polyol synthesizes the not fire-retardant soft foam materials of PU, and because the hydroxyl value of soybean oil is higher, the usage amount in formula is smaller, from
As can be seen that at most only using to 20% in embodiment.
The present invention relates to a kind of preparation side of soybean oil based polyurethanes flame retarded rigid foams for application number 201510195699.6
Method, polyurethane flame-retardant foam are made up of component A and B component.Its component A includes：Polyalcohol, foaming agent, catalyst, B component are
Isocyanates.Water is added as foaming agent, after stirring, B component toluene di-isocyanate(TDI) is added and stirs.Then put
Enter baking oven foaming, soybean oil based polyurethanes flame retarded rigid foams are just obtained after a period of time.The method is used primarily in polyurethane resistance
Fire rigid foam to prepare, synthetic method and the use of raw material is not Normal practice, it is difficult to produce qualified product.
The content of the invention
It is an object of the invention to provide a kind of preparation technology is simple, foam plyability is good, and outward appearance and environmental protection can reach
Biomass-based flame-retardant polyurethane flexible sponge foam of polyurethane foam application requirement and preparation method thereof.
The present invention technical solution be：
A kind of biomass-based flame-retardant polyurethane flexible sponge foam, it is characterized in that：By with (a) fire-retardant modified epoxy soybean oil
Polyalcohol, (b) polymer polyatomic alcohol are primary raw material, in response type or the catalyst of low smell, are physically and/or chemically foamed
Under agent, foam stabiliser or fire retardant effect, the environmentally friendly recyclable organism of generation is polymerize with (c) isocyanate component mixed foaming
Matter flame-retardant polyurethane flexible sponge foam.
Described fire-retardant modified epoxy soybean oil polyol is flame retardant epoxy soybean oil-base polyether polyol, and its hydroxyl value exists
20‐250mgKOH/g；Can be carried out with epoxidized soybean oil and small molecule reactive flame retardant in the presence of base catalyst
Ring-opening reaction, then reacted with epoxyalkane, the flame retardant epoxy soybean oil-base polyether polyol of high functionality is made.
Described polymer polyatomic alcohol is that melamine resin is grafted soft bubble polymer polyatomic alcohol；Can be with general polyether polyols
Polyethers (typically with general soft bubble polyether triol, high activity polyether), encrypts polyimide resin, in 100 degree or so and nitrogen based on alcohol
Graft polymerization is carried out under protection to form.
Described isocyanate component is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, the more isocyanides of more phenyl
One or more in acid esters or two or polyisocyanates of modification.
The weight ratio of described primary raw material (a) (b) (c) is (0-100)：(100‐0)：(20-70), isocyanate index
Index is 90-150.
Described response type catalyst is N, N- dimethylethanolamines, diethanol amine, tetramethylethylenediamine, triethanolamine or
At least one of triethylamine；The low smell catalyst be triethylenediamine, stannous octoate, dibutyl tin laurate or
One or more in two dibutyitin maleates.
Described CBA is water；Described foam stabiliser is silicone surfactant, silicon class surface-active
It is one or two kinds of in agent；Described fire retardant is three (2- chloroethyls) phosphates, three (2- chloropropyls) phosphates, triethyl phosphate
With the one or more of methyl-phosphoric acid dimethyl ester.
A kind of preparation method of biomass-based flame-retardant polyurethane flexible sponge foam, it is characterized in that：Utilize sponge multicomponent
Foaming machine mixes various raw material high-speed stirreds, is foamed on continuous foamed line, cures, shaping；Specifically comprise the following steps：
(1) by fire-retardant modified epoxy soybean oil polyol, polymer polyatomic alcohol, isocyanates, catalyst, foaming agent, bubble
Foam stabilizers are added separately in head tank；
(2) raw material pump is by each component feedstock transportation to foam mixing head, and after high-speed stirred mixes, it is continuous to be transported to foaming
Foamed on line, cure curing molding.
The biomass-based flame-retardant polyurethane flexible sponge foam of the present invention is given birth to by using renewable biomass raw material
Production, foam synthetic products are reduced to the dependency degree of oil coal resources, product price is stabilized, also reaches the mesh of environmentally friendly low-carbon
's.
With reference to embodiment, the invention will be further described.
Embodiment
It is further illustrated by the examples that follow the present invention, but the invention is not restricted to following examples, unless otherwise indicated,
Otherwise, all amounts provided with " number " and " percentage " are all construed as being by weight.Following material is used to produce
The polyurethane foamed material of embodiment：
The urethane raw brief introduction of table 1
The preparation method of biomass-based flame-retardant polyurethane flexible sponge foam, comprises the following steps：(1) it is flame retardant epoxy is big
Soya-bean oil polyalcohol A and polymer polyatomic alcohol, catalyst, foaming agent, foam stabiliser, fire retardant and isocyanate component；By under
Listed each component is transported to foaming die by measuring pump by the part by weight in table 2 in table 2, after high-speed stirred,
Even cloth produces several meters long of finished foam material on the brown paper of continuous foamed production line.Use the common skill in this area
Production line mixed foaming step prepares these foamed materials known to art personnel, after foam curing shaping, detects foaming properties.
The biomass-based flame-retardant polyurethane flexible sponge foam plastic formula of table 2
In embodiment, using PEPA and flame retardant epoxy soybean oil polyol as primary raw material.Regulation is such as needed to foam
Speed, it can adjust catalyst amount；Such as need to adjust foam density, the dosage of adjustable water.
By these crucial spumescences of apparent density, 25% indentation force deflection, horizontal firing speed, smoke density grade and smell
It can collect and contrast, what is had is better, and what is had is weaker.But it can be reached the most by the adjustment of the proportioning of each combination material
Suitable raw material proportioning, performance is up to standard, cost optimization.
The biomass-based flame-retardant polyurethane flexible sponge foam parameter of table 3
Foregoing embodiments of the invention are for the purpose of illustrative and not limiting property.Embodiment described in text can be
Various change or modification are carried out on the premise of without departing from the spirit and scope of the present invention, this be to those skilled in the art it is aobvious and
It is clear to.The scope of the present invention is defined by the following claims.
Claims (8)
1. a kind of biomass-based flame-retardant polyurethane flexible sponge foam, it is characterized in that：By with (a）Fire-retardant modified epoxy soybean oil is more
First alcohol, (b) polymer polyatomic alcohol are primary raw material, in response type or the catalyst of low smell, physically and/or chemically foaming agent,
Under foam stabiliser or fire retardant effect, the environmentally friendly renewable biomass of generation is polymerize with (c) isocyanate component mixed foaming
Flame-retardant polyurethane flexible sponge foam.
2. biomass-based flame-retardant polyurethane flexible sponge foam according to claim 1, it is characterized in that：It is described fire-retardant to change
Property epoxy soybean oil polyalcohol is flame retardant epoxy soybean oil-base polyether polyol, and its hydroxyl value is in 20-250mgKOH/g.
3. biomass-based flame-retardant polyurethane flexible sponge foam according to claim 1, it is characterized in that：Described polymer
Polyalcohol is that melamine resin is grafted soft bubble polymer polyatomic alcohol.
4. biomass-based flame-retardant polyurethane flexible sponge foam according to claim 1, it is characterized in that：Described isocyanic acid
Ester component is two or polyisocyanate of toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, polyphenyl polyisocyanate or modification
One or more in cyanate.
5. biomass-based flame-retardant polyurethane flexible sponge foam according to claim 1, it is characterized in that：Described main original
Material（a）（b）（c）Weight ratio be（0-100）：（100-0）：（20-70）, isocyanate index index is 90-150.
6. biomass-based flame-retardant polyurethane flexible sponge foam according to claim 1, it is characterized in that：Described reaction
Type catalyst is N, at least one in N- dimethylethanolamines, diethanol amine, tetramethylethylenediamine, triethanolamine or triethylamine
Kind；The low smell catalyst is triethylenediamine, stannous octoate, dibutyl tin laurate or two dibutyitin maleates
In one or more.
7. biomass-based flame-retardant polyurethane flexible sponge foam according to claim 1, it is characterized in that：Described chemistry
Foaming agent is water；Described foam stabiliser is one or two kinds of in silicone surfactant, silicon class surfactant；It is described
Fire retardant be three（2- chloroethyls）Phosphate, three（2- chloropropyls）Phosphate, triethyl phosphate and methyl-phosphoric acid dimethyl ester
One or more.
8. a kind of preparation method of the biomass-based flame-retardant polyurethane flexible sponge foam described in claim 1, it is characterized in that：Profit
Various raw material high-speed stirreds are mixed with sponge multicomponent foaming machine, foamed on continuous foamed line, are cured, shaping；Specific bag
Include following steps：
（1）Fire-retardant modified epoxy soybean oil polyol, polymer polyatomic alcohol, isocyanates, catalyst, foaming agent, foam is steady
Determine agent to be added separately in head tank；
（2）Raw material pump is by each component feedstock transportation to foam mixing head, after high-speed stirred mixes, is transported in foaming continuous lines
Foamed, cure curing molding.
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| CN201710753052.XA CN107417885A (en) | 2017-08-28 | 2017-08-28 | Biomass-based flame-retardant polyurethane flexible sponge foam and preparation method thereof |
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| CN201710753052.XA CN107417885A (en) | 2017-08-28 | 2017-08-28 | Biomass-based flame-retardant polyurethane flexible sponge foam and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003418A (en) * | 2019-04-24 | 2019-07-12 | 东莞市腾崴塑胶制品有限公司 | A kind of biopolyol sponge and preparation method |
| CN110041689A (en) * | 2019-04-19 | 2019-07-23 | 天津企辰聚氨酯有限公司 | A kind of polyisocyanurate foam and preparation method thereof |
| WO2019233151A1 (en) * | 2018-06-07 | 2019-12-12 | 浙江高裕家居科技有限公司 | Polyurethane composite material and preparation method therefor |
| CN111217983A (en) * | 2018-11-26 | 2020-06-02 | 韩国P&P株式会社 | Impregnated material containing biological dietary fiber composition and method for producing same |
| CN111285995A (en) * | 2020-03-31 | 2020-06-16 | 优尔爱(常州)医疗科技有限公司 | Hydrophobic polyurethane foam for nasal cavity hemostatic cotton and preparation method thereof |
| CN113881092A (en) * | 2021-11-07 | 2022-01-04 | 上海壳麦科技有限公司 | Preparation method of bio-based MDI synthetic sponge and bio-based pillow |
| CN113942160A (en) * | 2021-11-15 | 2022-01-18 | 梦百合家居科技股份有限公司 | Preparation method of flame-retardant non-temperature-sensitive memory foam |
| CN114479004A (en) * | 2022-02-28 | 2022-05-13 | 安徽太平海绵制品有限公司 | Anti-corrosion sponge and preparation method thereof |
| CN115160735A (en) * | 2022-08-19 | 2022-10-11 | 吉林大学 | Soybean oil epoxy resin porous acoustic material and preparation method thereof |
| CN116425938A (en) * | 2023-03-23 | 2023-07-14 | 江苏米尔化工科技有限公司 | Flame-retardant polyurethane soft foam with excellent mechanical properties and preparation method thereof |
| CN116987242A (en) * | 2023-09-26 | 2023-11-03 | 张家港市顾乐仕生活家居科技有限公司 | Low temperature sensitivity bio-based damping sponge |
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Cited By (15)
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|---|---|---|---|---|
| WO2019233151A1 (en) * | 2018-06-07 | 2019-12-12 | 浙江高裕家居科技有限公司 | Polyurethane composite material and preparation method therefor |
| CN111217983A (en) * | 2018-11-26 | 2020-06-02 | 韩国P&P株式会社 | Impregnated material containing biological dietary fiber composition and method for producing same |
| CN110041689A (en) * | 2019-04-19 | 2019-07-23 | 天津企辰聚氨酯有限公司 | A kind of polyisocyanurate foam and preparation method thereof |
| CN110041689B (en) * | 2019-04-19 | 2021-02-05 | 天津企辰聚氨酯有限公司 | Polyisocyanurate foam and preparation method thereof |
| CN110003418A (en) * | 2019-04-24 | 2019-07-12 | 东莞市腾崴塑胶制品有限公司 | A kind of biopolyol sponge and preparation method |
| CN111285995B (en) * | 2020-03-31 | 2022-04-22 | 优尔爱(常州)医疗科技有限公司 | Hydrophobic polyurethane foam for nasal cavity hemostatic cotton and preparation method thereof |
| CN111285995A (en) * | 2020-03-31 | 2020-06-16 | 优尔爱(常州)医疗科技有限公司 | Hydrophobic polyurethane foam for nasal cavity hemostatic cotton and preparation method thereof |
| CN113881092A (en) * | 2021-11-07 | 2022-01-04 | 上海壳麦科技有限公司 | Preparation method of bio-based MDI synthetic sponge and bio-based pillow |
| CN113942160A (en) * | 2021-11-15 | 2022-01-18 | 梦百合家居科技股份有限公司 | Preparation method of flame-retardant non-temperature-sensitive memory foam |
| CN114479004A (en) * | 2022-02-28 | 2022-05-13 | 安徽太平海绵制品有限公司 | Anti-corrosion sponge and preparation method thereof |
| CN115160735A (en) * | 2022-08-19 | 2022-10-11 | 吉林大学 | Soybean oil epoxy resin porous acoustic material and preparation method thereof |
| CN115160735B (en) * | 2022-08-19 | 2024-05-17 | 吉林大学 | Soybean oil epoxy resin porous acoustic material and preparation method thereof |
| CN116425938A (en) * | 2023-03-23 | 2023-07-14 | 江苏米尔化工科技有限公司 | Flame-retardant polyurethane soft foam with excellent mechanical properties and preparation method thereof |
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