CN106496499A - Soft foam material of a kind of low abnormal smells from the patient environment-friendly polyurethane and its preparation method and application - Google Patents
Soft foam material of a kind of low abnormal smells from the patient environment-friendly polyurethane and its preparation method and application Download PDFInfo
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- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/14—Manufacture of cellular products
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- 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
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6552—Compounds of group C08G18/63
- C08G18/6558—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6564—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6552—Compounds of group C08G18/63
- C08G18/6558—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/657—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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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- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The present invention relates to soft foam material of a kind of low abnormal smells from the patient environment-friendly polyurethane and its preparation method and application.The present invention coordinates the flexible polyurethane foam material of polyether polyol and polymer polyatomic alcohol of low abnormal smells from the patient etc., preparation to have obvious effect in terms of abnormal smells from the patient and TVOC is reduced by components such as the catalyst combination using low abnormal smells from the patient, low-volatile silicone oil and gas catches.In combination material bulk foam process and molding foaming technique that the present invention is provided, with the features such as process stabilizing, quick ripening, low production process abnormal smells from the patient, environmental protection.
Description
Technical field
The invention belongs to soft polyurethane foam technical field, and in particular to a kind of soft foam material of low abnormal smells from the patient environment-friendly polyurethane and its
Preparation method and application.
Background technology
Polyurethane flexible foam is due to its special open-celled structure so as to density low, elastic recovery is good, sound-absorbing, thoroughly
The performances such as gas, insulation, main usess include the mat material such as furniture mat material, mattress, vehicle seat medicated cushion, also include industry and the people
Use, also use as filtering material, packing, ornament materials, deadener, packaging material and heat-barrier material etc..
TVOC is the English abbreviation of VOC, and World Health Organization (WHO) (WHO, 1989) organic to general volatile
The definition of compound (TVOC) is, the fusing point VOC of boiling point between 50～260 DEG C less than room temperature total
Claim.These VOCs include the materials such as formaldehyde, ammonia, ethylene glycol, esters.When in room, TVOC reaches finite concentration
When, headache, Nausea and vomiting, the symptom such as weak can be caused, even caused tics, stupor when serious, injured liver, kidney, brain
And nervous system, cause the serious consequences such as hypomnesis.With attention rate more and more higher of the people to environmental protection, soft polyurethane foam
The abnormal smells from the patient of release and TVOC contents also become more strictly to be limited.The TVOC main components of soft polyurethane foam include hydro carbons, halogen
For hydrocarbon, oxygen hydrocarbon and nitrogen hydrocarbon, for example benzene homologues, aldehyde material, organic chloride, freon series, organic ketone, amine, alcohol, ether, ester,
Acid and oil hydrocarbon compound etc..
Primary raw material used by existing soft polyurethane foam includes isocyanates, polyether polyol, foam rise catalyst, bubble
Foam gel catalyst, silicone oil etc., catalyst therein are particularly some traditional amines catalysts, can discharge in foaming process
Go out a large amount of abnormal smells from the patient volatile matters, it is impossible to meet the high-environmental of people, low abnormal smells from the patient, the low requirement distributed with TVOC.
The research worker such as Li Jian are prepared for environmental protection by coordinating other raw materials from low-unsaturation-degree, highly active polyethers
The low density foam of type, but still select traditional amines catalyst, the demand for meeting environmental protection that can not be real；Chinese public
Open and in patent CN104558492A, disclose a kind of automobile-used polyurethane interior trim foam of low abnormal smells from the patient high fire-retardance, main anti-by adding
Answer type fire retardant to reduce abnormal smells from the patient, but the abnormal smells from the patient and VOC of traditional catalyst generation are not improved；Chinese publication
The preparation method of low VOC content polyurethane foam is disclosed in CN101280518A, although can reduce foam to a certain extent
Abnormal smells from the patient, but technique is relative to become complicated.
There is presently no more effective method shadow can not be received soft polyurethane foam performance and processing and forming technology is ensured
On the premise of sound, while the abnormal smells from the patient and TVOC of soft polyurethane foam significantly can be reduced so as to meet wanting for environmental protection as far as possible
Ask.
The problem for how reducing soft polyurethane foam abnormal smells from the patient and VOC be now so that following primary study direction.
Content of the invention
The purpose of the present invention is to prepare a kind of flexible polyurethane foam material of low abnormal smells from the patient environmental protection, is designed simultaneously by rational formula
Gas catch used in formula, the flexible polyurethane foam material of preparation have obvious effect in terms of abnormal smells from the patient and TVOC is reduced.
Another object of the present invention is to provide a kind of method of the flexible polyurethane foam material for preparing the low abnormal smells from the patient environmental protection,
The method process stabilizing, ripening is quick, production process abnormal smells from the patient is low, environmental protection, it is adaptable to block foam process and molding foaming technique.
Another object of the present invention is to provide the flexible polyurethane foam material of the low abnormal smells from the patient environmental protection and is in has mat material, mattress, friendship
The purposes of logical instrument Chain cushion etc. aspect.
For realizing above goal of the invention, the technical solution used in the present invention is as follows：
A kind of soft foam material of low abnormal smells from the patient environment-friendly polyurethane, is prepared from including following components：
It is initiator by glycerol and/or trimethylolpropane that polyether polyol of the present invention is, oxirane, epoxy
The low-odor polyether polyol of propane ring-opening polymerisation.The degree of unsaturation of the polyether polyol is less than 0.05mol/kg, number
3000～6000, distribution is less than 1.05 to average molecular weight；The number-average molecular weight of heretofore described polyether polyol be 3000～
6000, wherein accounting of the ethylene oxide content in polyether polyol quality be 5～30wt%, the total matter based on polyether polyol
Amount.
Polyether polyol of the present invention includes but is not limited to Wanhua Chemical Group Co., Ltd.
F3135, the GEP-330N of Gaoqiao Petrochemical Company, can LeahFA-703, Shandong Lanxing Dongda Chemical Co., Ltd
EP-330NY, DOW3010th, group of EP-553, Wan Hua chemical company stock of Zibo Ju Feng emulsifying agents factory
Part company limitedF3156, blue star the east DEP-5631D of major company, the PPG-5623 of shell and Gaoqiao Petrochemical Company
One or more in GEP-560s etc., preferably joint-stock company of group of Wan Hua chemical companiesF3156 or
F3135.
Polymer polyatomic alcohol of the present invention be by styrene, acrylonitrile and basic polyether polyhydric alcohol mixture from
By the low abnormal smells from the patient and the polymer polyatomic alcohol of low residual monomer that carry out glycerol polymerization preparation in the presence of base initiator.Wherein, described
, in 2000-5000, oxirane 5～20wt% of accounting, based on polyether polyol for the number-average molecular weight of basic polyether polyhydric alcohol
Gross mass.In the present invention, polymer polyatomic alcohol, solids content is 10～50wt%, and the styrene-content of residual is less than 10ppm,
The acrylonitrile content of residual is less than 10ppm.
Heretofore described polymer polyatomic alcohol mainly includes joint-stock company of group of Wan Hua chemical companies
Joint-stock company of group of POP2140, Wan Hua chemical companyPOP2045, the GPOP-H45Y of Gaoqiao Petrochemical Company, Gaoqiao Petrochemical Company
GPOP-2045 and can LeahKE880S etc. in one or more, preferred group of Wan Hua chemical companies share
Company limitedPOP2140 or POP2045.
Pore-creating agent of the present invention is oxypropylene-oxyethylene copolyether and/or oxyalkylene-copolymeric siloxane
Thing, preferably oxypropylene-oxyethylene copolyether, the oxypropylene-oxyethylene copolyether is sealed by oxirane
The polyoxypropylene polyol at end, proportion of primary OH groups in 60-80wt%, number-average molecular weight in 2000-4000, preferred perforate
Agent is included but is not limited in the LEP-642 of the grand magnificent Chemical Group of GK-350D, the TA-350 of SK companies of Korea and Shandong of high bridge
One or more.
Carbon monoxide-olefin polymeric of the present invention is the catalyst combination of low abnormal smells from the patient, using containing active hydrogen group, and energy
The catalyst combination of the NCO group reaction in enough and isocyanates, so that evade the volatilization of small molecule amine substance.Preferably urge
Agent compositionss Air products companiesNE 300、NE317、NE
1070、NE 1082, Hunstman companiesZF-10、ZR-50、Z-131、DPA, dimethylaminoethoxyethanol, three (dimethylaminopropyl) amine, tetramethyl dipropyl
The two or more combination that alkene triamine, modified dimethyl cyclohexyl amine and acid seal are closed in triethylene diamine, preferred mass ratio isZF-10：NE1082=1:3-1:8 catalyst combination, more preferably mass ratio areZF-10：NE1082=1:4-1:7 catalyst combination.
Air products companiesNE 300 is the expansion type catalyst of scattered；NE 317 is the kicker of one scattered delay；NE 1070、NE
1082 is the gel catalyst of two different activities；ZF-10 is the double aminoethyl ethers of trimethyl hydroxyethylammonium, efficiently
Response type kicker, with low sporadic；ZR-50 is double (dimethylamino-propyl) isopropanolamines, reaction
Type gel catalyst, low sporadic；Z-131 andDPA is low abnormal smells from the patient, and response type gel is urged
Agent；The catalyst combination that the present invention is adopted and traditional blowing agent combination (double (dimethylamino second of such as expansion type catalyst A1
Base) ether and gel-type catalyst A33 triethylene diamines, stannous octoate) to compare, the catalyst combination of the present invention is low abnormal smells from the patient, anti-
Answer type, not volatile catalyst system, in catalyst can reactive group be grafted in foaming process in polyurethane molecular chain,
So as to amine substance will not be discharged in foam maturing process catalyst, small-molecule substance during use, will not be also produced
Toxicity release problem, meet the requirement of low abnormal smells from the patient, environmental protection, and new catalyst system cause foamable reaction more gentle,
More can significantly improve the mobility of foam, reduce the defect incidence rate of foamed product, while improve production efficiency.
In the present invention, the cross-linking agent is the alcohol and/or hydramine that two functional groups or trifunctional have active hydrogen group, bag
Include but be not limited to the one kind or many in diethanolamine, triethanolamine, trimethylolpropane, dipropylene glycol and 1,4- butanediols
Kind.
Silicone oil of the present invention is mainly low volatilization, the environment-friendly type surfactant of low abnormal smells from the patient,
B8773 LF2, the working width with non-constant width have ultralow haze value, it is adaptable to various systems in secret room test；
The UF-5880 of OSIC has extremely low VOC, while there is splendid technological operation tolerance, it is adaptable to different types of foaming work
Skill, UF-5366 are applied to the low VOC silicone oil that high resilience molding and block steep sponge, to TDI and TDI/MDI mixed systems, have very
Strong foam stabilizing effect, eliminate defective workmanship, the low abnormal smells from the patients of UF-6680, be applied to block steep sponge system；
Wound preferably won by silicone oil of the present inventionB 8745 LF2、B8736
LF2、One or more in UF-5880, UF-5366 and UF-6680 of B8773 LF2 and-OSIC.
In the present invention, the foaming agent is physical blowing agent dichloromethane, HCFC-141b, liquid CO 2 and chemistry
One or more in foaming agent water, preferably water and/or dichloromethane.
Gas catch of the present invention includes nanometer porous physical absorption material and with many amino structures
Chemical absorbing material.The physical absorption material includes but is not limited in activated carbon, white carbon, activated silica gel and aluminium oxide
Plant or multiple；The chemical absorbing material with many amino structures is selected from the aldehydes agent for capturing with hydrazine structure, structural formula
As follows：
Wherein R1For straight or branched C3-C10 alkyl or alkoxyl, preferably straight or branched C5-C8 alkyl or alkoxyl；
R2For H or straight or branched C1-C5 alkyl, preferably H or CH3；
Integers of the n for 5-20, the preferably integer of 12-18, it can be occurred under conditions of polyurethane foam heat release with formaldehyde
Dehydration, reaction equation are as follows:
HCHO+H2N-NH-→H2C=N-NH-
FM-505 the and/or Air Product of the preferred Huntsman of the chemical absorbing material with many amino structures
XFAE18002；
In the present invention, preferred gas catch is white carbon and FM505, and more preferably mass ratio is 10:1～20:1
White carbon and FM505.
In the present invention, the gas catch is mainly played by physical absorption and chemical absorbing and is waved in reduction foam system
The effect of stimulating food concentration.Physical absorption due to using adsorbent there is loose structure, there is provided substantial amounts of specific surface area, from
And the purpose for being very easy to reach gas in absorbent foam；Chemical absorbing is due to the chemicals with many amino structures that use
Matter, due to its special chemical constitution, can occur chemistry with aldehyde material anti-under the heat condition produced by foaming process
Aldehydes agent for capturing is should be used as, the purpose of aldehyde material in foam is reduced.Both physical absorption and chemical absorbing common
In the presence of, the content of aldehydes, benezene material in foam greatly can reduce.
Isocyanates of the present invention be toluene di-isocyanate(TDI) (TDI), polyphenyl polymethylene polyisocyanates and
One or more in polyether-modified methyl diphenylene diisocyanate；It is preferred that 10%:90%-90%:More than 10%, how sub- phenyl is
Methyl polyisocyanates and toluene diisocyanate mixture, with polyphenyl polymethylene polyisocyanates and toluene diisocynate
The weight of ester and meter, or polyether-modified methyl diphenylene diisocyanate；More preferably Wanhua Chemical Group Co., Ltd.8019、8122 Hes7080、One kind in 1080
Or it is multiple.
The preparation method of the soft foam material of low abnormal smells from the patient environment-friendly polyurethane of the present invention, comprises the following steps：
(1) preparation of polyol component：Under heating condition, (80 DEG C) are proportionally by polyether polyol and polymer polyol
Alcohol mixes in a kettle., and gas catch is slowly added to, and treats that temperature is cooled to room temperature, and then sequentially adds silicone oil, crosslinking
Agent, pore-creating agent, carbon monoxide-olefin polymeric and foaming agent, after 0.5～1.0h of mixing, sealing preserve；
(2) foam：Under room temperature, proportionally by polyol component and the mixing of isocyanates, pour into and send out
Foam is taken out after terminating and carries out ripening by bubble, foaming.
In the present invention in the preparation process of polyol component polyether polyol and polymer polyatomic alcohol in 50～80 DEG C anti-
Answer stirring mixing 0.5h-1h, 2000～3000r/min of stir speed (S.S.) in kettle；Add gas catch after, continue stirring 0.5～
After 1.0h, waiting temperature is cooled to room temperature.
Used as preferred scheme, in foaming process, polyol component is 1.3 with the mass ratio of isocyanates:1～3.2：1.
In the present invention, foaming process is carried out under the high-speed stirred of 2000～3500r/min, mold temperature be 25～
60 DEG C, foam is taken out after terminating and carries out ripening under lucifuge ventilation condition by 3～8min of foamed time, foaming, and the curing time leads to
It is often 2～4 days.
The soft foam material of low abnormal smells from the patient environment-friendly polyurethane that the present invention is prepared, carries out foam abnormal smells from the patient survey using PV3900 standards
Examination, using VDA 278, HJ/T 400-2007 carry out benzene class in foam, aldehyde material and TVOC tests, the TVOC of final foam
And aldehyde material is decreased obviously, while optimization formula is also apparent from the abnormal smells from the patient for reducing foamed product.
In the present invention, the polyether polyol of the low abnormal smells from the patient of employing, the polymer polyatomic alcohol of low abnormal smells from the patient and low residual monomer, anti-
Answer the flexible polyurethane foam material of the preparations such as catalyst combination, low-volatile silicone oil and the gas catch of type reduce abnormal smells from the patient and
There is obvious effect in terms of TVOC.
The soft foam material of low abnormal smells from the patient environment-friendly polyurethane of the present invention can be applicable to mat material field, including but not limited to furniture
The fields such as mat material, medical mat material, vehicle seat, clothing, toy, case and bag, with low abnormal smells from the patient, the low effect for distributing meets
The requirement of environmental protection, is preferably applied in automotive seat, mat material, soft furniture mat material.
Compared with prior art, the present invention has following beneficial effect：
(1) polymer polyatomic alcohol that the present invention is adopted, itself level of residual monomers is low, and (styrene-content of residual is less than
10ppm, the acrylonitrile content of residual are less than 10ppm), polyether-modified isocyanates have low volatility, drop from raw material
The low abnormal smells from the patient of foam；
(2) employing can reduce the combination catalyst of polyurethane foam abnormal smells from the patient, can evade the release of traditional amines catalyst,
Simultaneously can significantly reduce the abnormal smells from the patient of system, preferred catalyst combination (ZF-10：Z-
131=1:4～1.7) be conducive to being obviously improved system ground mobility, reduce the ratio of defects of product, improve production efficiency；
(3) gas catch can pass through under the collective effect of physical absorption and chemical absorbing, respectively to system in benzene
Based compound and aldehyde material have the effect for reducing concentration well, it will be apparent that reduce abnormal smells from the patient and TVOC, and will not be to bubble
The physical property of foam has a negative impact.
Specific embodiment：
In conjunction with specific examples below, the present invention will be further described, but the present invention is not limited to the embodiment listed,
Also include all any known changes in right in the present invention.
In the present invention, the method for the evaluation and test of foam abnormal smells from the patient using PV 3900, Odor Evaluations evaluate teachers according to smelling by 5
Foam abnormal smells from the patient scored (1 grade：Imperceptible scent of；2 grades：Feel faint odor, but nothing makes us uncomfortable；3 grades：Bright
Show and feel abnormal smells from the patient, but nothing makes us uncomfortable；4 grades：Make us uncomfortable；5 grades：Strong uncomfortable；6 grades：Intolerable), finally take
The result that meansigma methodss are passed judgment on as oder levels；Using VDA 278, HJ/T 400-2007 carry out benzene class, aldehyde material in foam
And TVOC tests.
F3156：Average functionality 3, number-average molecular weight are 3000, hydroxyl value 56, and ten thousand magnificent chemical groups shares have
Limit company.
F3135：Average functionality 3, number-average molecular weight are 5000, hydroxyl value 34, and ten thousand magnificent chemical groups shares have
Limit company；.
POP2140：Wanhua Chemical Group Co., Ltd.；
POP2045：Solid content is 43wt%, Wanhua Chemical Group Co., Ltd.；
8019、8122 Hes7080,
1080：Wanhua Chemical Group Co., Ltd..
B 8745LF2、B8736、B8773：Evonik
Industries AG companies；
UF-5880、UF-5366、UF-6680：OSIC companies；
D8154：Momentive companies；
NE 300、NE 1082：Air product companies；
FM505：Huntsman companies；
White carbon：Wacker companies；
Aerosil：10～40nm of mean diameter, Ying Chuan company；
Embodiment 1
(1) preparation of polyol component：According toF3135：POP2140=4:1 mass ratio, point
Another name takes80 weight portions of F3135 and20 weight portions of POP2140 mix in a kettle., then heat
Under the conditions of (80 DEG C) interpolation gas catch (white carbons：FM505=10:1) 2 parts, stirring mixes dissolves to catch, is cooled to
Room temperature, weighs 1 part of silicone oil GK350D successively, after being sufficiently mixed, adds 4.2 parts of water, 0.72 part of UF5880, diethanolamine
0.71 part, catalyst combination (ZF-10：NE1082=1:6) 1.2 parts, mix 0.5～1.0h
Afterwards, sealing preserve；
(2) foam：Under room temperature, by 71 parts8019 are added in polyether polyatomic alcohol component, in 2500r/min
Mix 8～15s under the high-speed stirred of～3000r/min, pour in mould rapidly and foamed, foam is taken out after terminating by foaming
Carry out ripening.
Embodiment 2-7
Preparation method is substantially the same manner as Example 1, and formula table and reaction condition refer to table 1.
Comparative example 1-3
Foam preparation processes are substantially the same manner as Example 1, and each component scale refers to table 1.
In table 1, data are weight portion if no special instructions.
1 comparative example of table and Example formulations
Performance test is carried out to flexible polyurethane foams prepared by above-described embodiment and comparative example, test result refers to table 2.
2 foaming properties index of table：
Above it can be seen that product flexible polyurethane foam material prepared by the present invention can ensure that there is excellent physical property
On the basis of energy, hence it is evident that reduce the abnormal smells from the patient and TVOC of flexible polyurethane foam material, greatly meet the demand of environmental protection.Process stabilizing,
Ripening is quick, production process abnormal smells from the patient is low, environmental protection process, and the technique of the material of preparation is applied to block foam process and mould
Modeling foam process, purposes are also widely used in the mat material such as furniture mat material, mattress, vehicle seat medicated cushion.
Claims (10)
1. a kind of soft foam material of low abnormal smells from the patient environment-friendly polyurethane, is prepared from including following components：
2. the soft foam material of low abnormal smells from the patient environment-friendly polyurethane according to claim 1, it is characterised in that：Described gas catch
Including nanometer porous physical absorption material and the chemical absorbing material with many amino structures；
The chemical absorbing structure of matter formula is：
R in formula1Straight or branched alkyl or alkoxyl for C3-C10, the preferably straight or branched alkyl of C5-C8 or alkoxyl；
R2For the straight or branched alkyl of H or C1-C5, preferably H or CH3；Integers of the n for 5-20, the preferably integer of 12-18；
The XFAE18002 of the FM-505 and/or Air Product of the preferred Huntsman of the chemical absorbing material；
Preferably, the physical absorption material includes one or more in activated carbon, white carbon, activated silica gel and aluminium oxide；
Preferred gas catch is white carbon and FM505, and more preferably mass ratio is 10:1～20:1 white carbon and
FM505.
3. the soft foam material of low abnormal smells from the patient environment-friendly polyurethane according to claim 1 and 2, it is characterised in that：The catalyst group
Compound is Air products companies Hunstman companies Dimethylaminoethoxyethanol, three
Close in triethylene diamine two kinds of (dimethylaminopropyl) amine, tetramethyl dipropylenetriamine, modified dimethyl cyclohexyl amine and acid seal with
On combination, preferred mass ratio is Catalyst group
Compound, more preferably mass ratio are Catalyst combination
Thing.
4. the soft foam material of low abnormal smells from the patient environment-friendly polyurethane according to any one of claim 1-3, it is characterised in that：Based on poly-
The gross weight of compound polyhydric alcohol, the solids content of the polymer polyatomic alcohol is 10～50wt%, in the polymer polyatomic alcohol
Styrene-content is less than 10ppm, and acrylonitrile content is less than 10ppm；
Preferred polymer polyatomic alcohol includes joint-stock company of group of Wan Hua chemical companies The GPOP-H45Y of Gaoqiao Petrochemical Company, the GPOP-2045 of Gaoqiao Petrochemical Company and can be in the KE880S of Leah
One or more, preferred Wan Hua chemical companies Group Plc Or
5. the soft foam material of low abnormal smells from the patient environment-friendly polyurethane according to any one of claim 1-4, it is characterised in that：Described poly-
The degree of unsaturation of ethoxylated polyhydric alcohol is less than 0.05mol/kg, and 3000～6000, molecular weight distribution is less than 1.05 to number-average molecular weight；
Preferably, described polyether polyol includes Wanhua Chemical Group Co., Ltd. High bridge stone
The GEP-330N of change, can LeahThe EP- of Shandong Lanxing Dongda Chemical Co., Ltd
330NY, DOW'sGroup of EP-553, Wan Hua chemical company share of Zibo Ju Feng emulsifying agents factory has
Limit companyBlue star the east DEP-5631D of major company, the PPG-5623 of CSPC and Gaoqiao Petrochemical Company
GEP-560s in one or more, more preferably group of Wan Hua chemical companies joint-stock companyOr
6. the soft foam material of low abnormal smells from the patient environment-friendly polyurethane according to any one of claim 1-5, it is characterised in that：Described open
Hole agent is oxypropylene-oxyethylene copolyether and/or oxyalkylene-silicone copolymers, preferably oxypropylene-oxyethylene
Copolyether；The oxypropylene-oxyethylene copolyether is the polyoxypropylene polyol blocked by oxirane, primary hydroxyl
Base content includes the GK-350D of high bridge, Korea in 60-80wt%, number-average molecular weight in 2000-4000, preferred pore-creating agent
One or more in the LEP-642 of the grand magnificent Chemical Group of the TA-350 of SK companies and Shandong.
7. the soft foam material of low abnormal smells from the patient environment-friendly polyurethane according to any one of claim 1-6, it is characterised in that：The silicon
Grease separation is from Evonik Industries AG's And UF-5880, UF-5366 of OSIC
With one or more in UF-6680.
8. the soft foam material of low abnormal smells from the patient environment-friendly polyurethane according to any one of claim 1-7, it is characterised in that：Described different
Cyanate is toluene di-isocyanate(TDI), poly methylene poly phenyl poly isocyanate and polyether-modified methyl diphenylene diisocyanate
In one or more；It is preferred that 10%:90%-90%:10% poly methylene poly phenyl poly isocyanate and toluene diisocynate
Ester admixture, by the weight of poly methylene poly phenyl poly isocyanate and toluene di-isocyanate(TDI) and in terms of, or polyether-modified hexichol
Dicyclohexylmethane diisocyanate；More preferably Wanhua Chemical Group Co., Ltd.With
In one or more.
9. the preparation method of the soft foam material of low abnormal smells from the patient environment-friendly polyurethane any one of claim 1-8, including following step
Suddenly：
(1) preparation of polyol component：Proportionally by polyether polyol and polymer polyatomic alcohol in reactor under heating condition
Middle mixing, gas catch is slowly added to, and is treated that temperature is cooled to room temperature, and then is added pore-creating agent, carbon monoxide-olefin polymeric, silicon
Oil, cross-linking agent and foaming agent, uniformly after 0.5～1.0h of mixing, sealing preserve；
(2) foam：Under room temperature, proportionally polyol component is mixed with isocyanates, pour in mould and foamed, foamed
After end taking out foam carries out ripening.
10. the soft foam material of low abnormal smells from the patient environment-friendly polyurethane any one of claim 1-8 and according to 9 methods described system of right
The soft foam material of the standby low abnormal smells from the patient environment-friendly polyurethane for obtaining is in furniture mat material, medical mat material, vehicle seat, clothing, toy, case
The purposes in bag field, the preferably purposes in automotive seat, soft furniture mat material.
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|---|---|---|---|
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| CN112322026A (en) * | 2020-10-12 | 2021-02-05 | 万华化学（北京）有限公司 | Polyurethane material and polyurethane foam |
| CN113165318A (en) * | 2018-09-25 | 2021-07-23 | 普罗普里特公司 | Composite foam article |
| CN113402693A (en) * | 2021-06-29 | 2021-09-17 | 广州亚伊汽车零部件有限公司 | Formula and preparation method of high-resilience foaming material |
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