CN110343227A - A kind of hard polyurethane foams of extremely-low density and preparation method thereof - Google Patents
A kind of hard polyurethane foams of extremely-low density and preparation method thereof Download PDFInfo
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- CN110343227A CN110343227A CN201910732877.2A CN201910732877A CN110343227A CN 110343227 A CN110343227 A CN 110343227A CN 201910732877 A CN201910732877 A CN 201910732877A CN 110343227 A CN110343227 A CN 110343227A
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
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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
- C08G18/487—Polyethers containing cyclic 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
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- 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
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- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
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- 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
- C08J9/08—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 developing carbon dioxide
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- 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
- C08J9/141—Hydrocarbons
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- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/20—Ternary blends of expanding agents
- C08J2203/204—Ternary blends of expanding agents of chemical foaming agent and physical blowing agents
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
It is respectively pre-mixed uniformly using pentane and butane as the hard polyurethane foams of the extremely-low density of foaming agent by component A and component B the present invention relates to a kind of, then, foaming uniform through mechanical mixture is prepared by component A and component B；Wherein, by weight, component A includes: Pluronic polyols, and 100 parts；Pentane, 4~15 parts；Catalyst, 1~5 part；Organic silicon surfactant, 1~5 part；Water, 1~2.5 part；Nucleating agent, 0~3 part；Combination B includes: butane, and 2~12 parts；Polyisocyanates, 120~210 parts；Above-mentioned each raw material is on the basis of 100 parts of Pluronic polyols.Foam cell obtained is fine and smooth, and uniformly thermal coefficient is small, and compressive strength is high, high comprehensive performance.Disclosed herein as well is the preparation methods of above-mentioned hard polyurethane foams.
Description
Technical field
The present invention relates to hard polyurethane foams of a kind of extremely-low density and preparation method thereof, more specifically to one kind
Use pentane and butane for hard polyurethane foams of extremely-low density of foaming agent and preparation method thereof.
Background technique
Hard polyurethane foams (hereinafter referred to as hard bubble) have heat-proof quality is excellent, sound insulation, insulation, light, specific strength is high,
The features such as processing performance is good is widely used as keeping the temperature cold insulation material.It, need to be to foam in order to reach better adiabatic heat insulating effect
The physical blowing agent of a certain amount of low boiling point, low thermal conductivity is added in material.Unfortunately, traditional polyurethane foams one
Fluoro trichloromethane (CFC-11) can seriously destroy ozone layer.After Montreal protocol is signed within 1987, various countries are unfolded one after another
The research of CFC-11 substitution foaming agent.After Kyoto Protocol is signed within 1997, people start to focus on protecting ozone layer simultaneously
With reduce greenhouse effects, it is expected that develop zero ozone depletion dive value (ODP) and zero global warming potential (GWP) foaming agent
To cope with the environmental problem that the whole world is got worse.
Compared with halogenated hydrocarbon foaming agent, alkanes foaming agent (such as pentane, butane) halogen-free atom, ODP zero,
GWP is approximately zero, environmentally friendly, relative low price, is one of ideal foaming agent alternative solution.
However, pentane boiling point is higher and has certain plasticity, easily make foam size bad stability.Ordinary circumstance is logical
The dimensional stability for improving foam density to guarantee foam is crossed, this but increases the production cost of foam.On the other hand, pentane exists
Dissolubility in polyalcohol is poor, and dosage is limited in formula.
Butane dissolubility in polyalcohol is poor, it is less be used for hard polyurethane foams, and its boiling point it is relatively low (normal butane
Boiling point is -0.5 DEG C, and the boiling point of iso-butane is -11.7 DEG C), the requirement to operating procedure is tightened up, when individually using butane foaming
When, they are easy to escape from reaction mass, cause foam surface stomata to increase, bring adverse effect to foaming properties.
The density of hard polyurethane foams and production cost are closely related.But foam density is reduced, foamy body will be brought
The series of defect such as reduction, dimensional stability variation.
Summary of the invention
The present invention can overcome above-mentioned deficiency, and it is good ultralow that comprehensive performance is made using pentane and butane as physical blowing agent
Foam production cost is effectively reduced in the foam of density, and the foam has extremely-low density and environment friendly simultaneously.On reaching
Target is stated, first offer first scheme, specific technical solution:
A kind of hard polyurethane foams of extremely-low density, the foam are respectively to be pre-mixed by component A and component B uniformly,
By component A and component B, foaming uniform through mechanical mixture is prepared again, wherein by weight,
Component A includes:
(1) Pluronic polyols, 100 parts, including: polycarbonate polyol is 3~50 parts, i.e. 100 parts of composite multi-components
It include 3~50 parts of polycarbonate polyols in alcohol；
(2) pentane, 4~15 parts；
(3) catalyst, 1~5 part；
(4) organic silicon surfactant, 1~5 part；
(5) water, 1~2.5 part；
(6) nucleating agent, 0~3 part；
Combining B includes:
(1) butane, 2~12 parts,
(2) polyisocyanates, 120~210 parts.
Above-mentioned each raw material is on the basis of 100 parts of Pluronic polyols.
Component A is made in pentane and Pluronic polyols premix by the present invention, and component is made in butane and polyisocyanates premix
B, then by component A, B mixed foaming, the excellent hard polyurethane foams of processability.Applicant it has been investigated that: it is more under low temperature
Isocyanates and butane have good compatibility, and the addition of nucleating agent can be effectively improved the foam structure of foam, improve bubble
Foam comprehensive performance.Contain a large amount of carbonyl in the molecular structure of polycarbonate polyol, intermolecular cohesive energy is big, can be foam
Material strips carry out excellent mechanical property, make foam intensity still with higher in the lesser situation of density.By above-mentioned compounding,
The disadvantage of above-mentioned raw materials respectively can be overcome, farthest play their synergistic function, extremely-low density is finally made
Hard polyurethane foams.
In above-mentioned hard polyurethane foams, Pluronic polyols hydroxyl value is 250~550mg KOH/g in the component A, by multiple
Closing polyol weight part is 100 parts of meters, and the Pluronic polyols includes that the polycarbonate that hydroxyl value is 100~350mg KOH/g is more
3~50 parts of first alcohol, hydroxyl value are 0~97 part of polyether polyol of 120~600mg KOH/g, and hydroxyl value is 100~450mg KOH/g
0~50 part of polyester polyol, hydroxyl value is 0~20 part of vegetable oil polyol of 350~650mg KOH/g, hydroxyl value is 300~
0~20 part of the Manny phase polyalcohol of 600mg KOH/g.
Polycarbonate polyol is the aliphatic polyol as made of carbon dioxide and epoxides copolymerization.The epoxidation
Object can be selected from one or more of ethylene oxide, propylene oxide, epoxy butane, oxepane or oxepane etc..The system
Preparation Method production cost is low, high financial profit, has a vast market foreground and environment protection significance.But polycarbonate polyol is added
After amount is more than 50 parts, adverse effect can be brought for foaming properties.
Polyether polyol in said components A is reacted by initiator and oxyalkylene, wherein oxyalkylene is selected from oxygen
Change one or more of propylene, ethylene oxide, butylene oxide, initiator is selected from the compound containing active hydrogen, such as: sucrose,
Glycerol, trimethylolpropane, pentaerythrite, sorbierite, xylitol, mannitol, methyl glucoside, ethylenediamine, triethanolamine, first
One or more of phenylenediamine etc..
Polyurethane foam hydrolysis, resistance to low temperature made from polyether polyol are good.High functionality, the polyethers of high hydroxyl value are more
First alcohol can provide enough degrees of cross linking and rigidity for foam.Low degree of functionality, the polyether polyol of low hydroxyl value can mention for foamed material
For good mobility.Existed using the pure and mild low degree of functionality of the polyether polyols of high functionality, high hydroxyl value, the polyether polyol of low hydroxyl value
While guaranteeing that there is good fluidity when good production, and guarantee the rigidity of product.
Polyester polyol in said components A is selected from aliphatic polyester polyols and/or aromatic polyester polyol, by low
The pure and mild low molecular acid of molecule (acid anhydride) is condensed, wherein low mass molecule alcohol can be selected from ethylene glycol, diethylene glycol, propylene glycol, the third three
One or more of alcohol, trimethylolpropane；Low molecular acid (acid anhydride) can be selected from cis-butenedioic anhydride, hexanedioic acid, phthalic acid anhydride, benzene
One or more of dioctyl phthalate, phthalic acid ester.
The foamed material hardness of polyester polyol preparation is high, and intensity is big, heat-resisting, oil resistance is good.
Vegetable oil-based polyols in said components A are reacted by initiator and oxyalkylene, wherein initiator can be with
Selected from one or more of vegetable oil such as castor oil, soybean oil, rapeseed oil, linseed oil.
Vegetable oil-based polyols can reduce the dosage of petroleum-based polyols, improve the hardness of foamed product, improve foam
Comprehensive performance.
Manny phase polyalcohol in said components A is with phenol or alkylphenol, formaldehyde or paraformaldehyde, alcohol amine compound
Mannich base is prepared in raw material, then carries out addition reaction with propylene oxide and/or ethylene oxide and be made.
Manny phase polyalcohol contains benzene ring structure and with autocatalytic nature, can be improved the mechanics and heat resistance of foamed material
Can, and reduce the dosage of catalyst.
It is each can to adjust Pluronic polyols in range provided herein according to actual needs by those skilled in the art
The proportion of raw material.
Pentane in said components A is selected from least one of pentamethylene, pentane or isopentane.
Compared with halogenated hydrocarbon foaming agent, alkanes foaming agent (such as pentane, butane) halogen-free atom, ODP zero,
GWP is low, environmentally friendly, relative low price, is one of ideal foaming agent alternative solution.
In above-mentioned hard polyurethane foams, the catalyst in the component A is selected from five methyl diethylentriamine, N, N- bis-
Methylbenzylamine, dimethyl cyclohexyl amine, triethylenediamine, tetramethylethylenediamine, N-methylmorpholine, N- methyldicyclohexyl amine,
Bis- (dimethylamino ethyl) ethers, N, N- dimethylaminoethanol amine, dimethylethanolamine, triethanolamine, tri- (dimethylamino of 1,3,5-
Propyl)-Hexahydrotriazine, 2,4,6- tri- (dimethylaminomethyl) phenol, 2- hydroxypropyl trimethyl ammonium formate, 2- hydroxypropyl
Two or more mixture in trimethylace tonitric ammonium or 2- hydroxypropyl trimethyl ammonium caprylate.
Those skilled in the art can according to actual needs compound above-mentioned catalyst, guarantee reaction balance and stability
Ground carries out.
In above-mentioned hard polyurethane foams, the organic silicon surfactant in the component A can be selected from poly dimethyl silicon
Oxygen alkane, polycyclic methylsiloxane, polysiloxanes-oxyalkylene copolymer, cationic silicone surfactant, anionic
Organic silicon surfactant, both sexes organic silicon surfactant.Specifically, can be selected from it is commercially available, such as Mitugao New Material Group
L-6861, L-6863, L-6866, L-6884, L-6900, L-6920 etc.；AK8805, the AK8806 of Mei Side company,
AK8810, AK8811, AK8818, AK8863 etc..
The molecular polarity of physical blowing agent pentane and butane used in the present invention is weak, and Pluronic polyols poor compatibility, they
It is easy to escape from cell wall in foaming process, causes foam surface defect, so that porosity increases.It is compound more in order to improve
First alcohol is to the dissolubility of these low pole foaming agents, and the present invention is using the organosilicone surfactant with good emulsifiability
Agent can effectively reduce the escape tendency of these physical blowing agents, and advantageously form at foamable reaction initial stage a large amount of fine and closely woven
Nuclei of bubbles, improve nucleation rate and the fine and closely woven degree of abscess, the phase can be improved the viscoplasticity of hole wall in the reaction, effectively inhibit bubble
The rupture in hole reduces surface pores, promotes foaming properties.
In above-mentioned hard polyurethane foams, the nucleating agent in the component A is perfluoroolefine and/or fluorine-containing ether, wherein complete
Fluoroolefins is selected from perfluor -1- butylene, perfluor -2- butylene, perfluorobutadiene, perfluoro-2-methyl-2-amylene, perfluor -4- methyl -
At least one of 2- amylene, octafluoro cyclopentene or perfluor -1- heptene；Fluorine-containing ether is selected from pentafluoropropyl group methyl ether, hexafluoro
Propyl methyl ether, hexafluoro isopropyl methyl ether, nona-fluoro butyl group methyl ether, nine fluorine isobutyl methyl ethers, nona-fluoro butyl group ethylether, nine
Fluorine isobutyl ethyl ether, bis-fluoro ethyls trifluoromethyl ethers, trifluoroethyl methyl ether, bis-fluoro ethyls tetrafluoro ethylether, difluoromethyl
Trifluoroethyl ether, bis- (trifluoroethyl) ethers, tetrafluoro ethyl-methyl ether, tetrafluoro ethyl diethyldithiocarbamate ether, tetrafluoro ethyl propyl ether, tetrafluoro second
At least one of base trifluoroethyl ether, four fluoro ethyl tetrafluoro propyl ethers or octafluoro amyl tetrafluoro ethylether.
Perfluoroolefine and fluorine-containing ether nucleating agent itself are also foaming agent, have and foam and be nucleated double effects.Their surfaces
Tension is low, easily gasifies in foaming process, forms the nuclei of bubbles of many uniformly dispersings, and foam is made to have finer and closely woven uniform abscess
Structure, so as to improve foaming properties.
In above-mentioned hard polyurethane foams, the polyisocyanates is unmodified polyisocyanates, or modified polyisocyanic acid
The mixture of the unmodified polyisocyanates and modified polyisocyanate of ester or arbitrary proportion.
Above-mentioned unmodified polyisocyanates is proposed with poly methylene poly phenyl poly isocyanate, can be selected from it is commercially available such as
The Suprasec 5005 of 44V-10L, 44V-20L, 44V-40L of Bayer company, Huntsman company, Suprasec 2085,
Suprasec 5000, the M20S of BASF AG, MR200, MR100 of Mitsui company, the PM2010 of Yantai Wanhua company,
PAPI27, PAPI135 etc. of PM200, Dow company.
Polyalcohol polarity is larger, is generally partial to water solubility, and unmodified isocyanates is oil-soluble, the two compatibility
It is poor.Above-mentioned modified polyisocyanate can improve its compatibility between polyalcohol, improve the comprehensive performance of foamed product；
Secondly, the stationarity of reaction can also be improved, and the reactivity decline of the NCO group in isocyanates after modified, Ke Yixiang
More catalyst are added in reaction system, promote the production efficiency of foam.
In view of production, packaging brought by modified polyisocyanate and transportation cost, those skilled in the art, Ke Yigen
According to cost control, working condition and convenience etc. because usually adjusting unmodified polyisocyanates and modified polyisocyanate in polyisocyanates
Ratio between cyanate.
In above-mentioned hard polyurethane foams, the mass fraction of the isocyanate group (NCO) of the modified polyisocyanate is
16.0%~30.0%, and the modified polyisocyanate be by containing active hydrogen compound and polyisocyanates through prepolymerization reaction
Obtained from modified polyisocyanate.
In above-mentioned hard polyurethane foams, the average functionality of the active hydrogen compounds is 2~3, active hydrogen compounds
Selected from the polycarbonate polyol that hydroxyl value is 100~350mg KOH/g, the polyester polyols that hydroxyl value is 120~300mg KOH/g
At least one of alcohol, polyether polyol that hydroxyl value is 200~500mg KOH/g.
Polyisocyanates is modified using the active hydrogen compounds of the application, not only improve improve polyisocyanates with
Compatibility between polyalcohol, and can guarantee that foam has enough mechanical strengths, facilitate the stable density for reducing foam.
Those of ordinary skill in the art can add other optional auxiliary agents concurrently or separately as needed also to obtain more preferably
Service performance, for example, age resister, plasticizer, preservative, fungicide, nucleating agent, antistatic agent, fire retardant, smog inhibit
Agent, crosslinking agent, pigment, filler etc..
Present invention also provides the preparation methods of above-mentioned hard polyurethane foams, comprising the following steps:
(1) component A is configured: in proportion by Pluronic polyols, pentane, catalyst, organic silicon surfactant, water and nucleation
Agent is added in mixing kettle, is stirred evenly, and component A is obtained, and material temperature control is 22~34 DEG C；
(2) it configures component B: butane, polyisocyanates being delivered to mixer in proportion, be uniformly mixed, obtain component B, expect
Temperature control is made as 6~18 DEG C；
(3) hybrid injection: component A and component B are passed through in proportion in high pressure machine gun head mixed injection closed mold, sufficiently
Reaction, die temperance control are 35~50 DEG C, and product can be prepared by hard polyurethane foams after demoulding.After foam-formed, measurement
The core density of foam when foamed material is just filled in a mold.And in actual use, according to production firm to spumescence
The requirement of energy is different, and crossing fill factor can be identified as 105%~135%.
Temperature is lower, and the viscosity of material is bigger, and mobility is poorer, influences the mixed effect between material each component.Temperature is got over
The mobility of height, foamed material is better, and foam density distribution is more uniform, can be using the complicated mold preparation in the intracavitary portion of type
Foam.But temperature is excessively high to will lead to low-boiling foaming agent rapid vaporization, material starting is too fast, is easy to make foam inside shape
At compared with macroscopic-void, foam mechanical property is influenced.Under same operation temperature, the component A containing higher boiling foaming agent pentane and contain
The component B of low-boiling foaming agent butane, the evolution rate of their foaming agents and the mobility of material mismatch, after the two mixing
Foaming effect is deteriorated, and foaming properties is caused to decline.The material temperature of component A containing higher boiling foaming agent pentane in the present invention is controlled
It is 22~34 DEG C, the material temperature of the component B containing low-boiling foaming agent butane is controlled as 6~18 DEG C, each by strictly limiting
The material temperature of component can effectively play the synergistic effect between the big foaming agent of both boiling point differences, improve foam jointly
Performance, the foam surface porosity obtained is low, is still able to maintain good dimensional stability at low temperature.
To guarantee that best synergistic effect can be reached between component A and component B, the temperature difference between component A and component B
It is best >=9 DEG C.
In general, compared with prior art, the invention has the characteristics that:
1, extremely-low density hard polyurethane foams Density Distribution prepared by the present invention is uniform, and specific strength is high, high/low temperature size
Stability is good, can effectively reduce injection volume, reduce cost；
2, the present invention can greatly improve foam by the temperature of feed liquid of the reduction containing low boiling point physical blowing agent butane
Surface defect；
3, hard polyurethane foams prepared by the present invention are using pentane and butane as physical blowing agent, and ODP zero, GWP is extremely low,
It is environmentally friendly.
Specific embodiment
For a better understanding of the present invention, the contents of the present invention are described in further detail below with reference to embodiment, this place
The embodiment of description is only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.Particular technique is not specified in embodiment
Or condition, it can be carried out according to well-known technique in the art.
The density of foam, thermal coefficient, compressive strength, expansion rate and high/low temperature size changing rate are pressed respectively in the present invention
According to standard GB/T/T 6343-2009, GB/T 3399-1982, GB/T 8813-2008, GB/T 20673-2006, GB/
T8811-2008 is measured, wherein core density refers to the closed mold that the injection of formation of foam composition is had some strength
Foaming in (1100 × 300 × 50mm), after foam-formed taking-up, foam removes the core concentration of epidermis.
Embodiment 1
Component A: feed liquid temperature is 22 DEG C,
Pluronic polyols: hydroxyl value 430mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 100~300mgKOH/g, 3 parts；
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 430~520mgKOH/g, 50 parts；
Polyether polyol B: sorbeth polyalcohol, hydroxyl value be 380~440mgKOH/g, 37 parts；
Polyether polyol C: glycerin polyether polyalcohol, hydroxyl value be 340~400mgKOH/g, 10 parts；
Catalyst: 0.6 part of pentamethyl-diethylenetriamine；0.4 part of triethylenediamine；(the dimethylamino third of 1,3,5- tri-
Base) 0.5 part of-Hexahydrotriazine；
Organic silicon surfactant: 1.5 parts of L-6863,0.5 part of L-6861；
Water: 1.8 parts；
Pentane: 12 parts, including 6 parts of pentamethylene, 6 parts of pentane；
Nucleating agent: 2.0 parts of perfluor -1- butylene；
Component B: feed liquid temperature is 6 DEG C,
Butane: 5 parts of iso-butane；
Unmodified polyisocyanates: 5005,138 parts of Suprasec；
35 DEG C of mould temperature, demoulding time 10min.
Embodiment 2
Component A: feed liquid temperature is 30 DEG C,
Pluronic polyols: hydroxyl value 450mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 150~300mgKOH/g, 10 parts；
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 450~550mgKOH/g, 60 parts；
Polyether polyol B: phenylenediamine polyether polyol, hydroxyl value be 360~440mgKOH/g, 10 parts；
Manny phase polyalcohol: hydroxyl value be 380~480mgKOH/g, 20 parts；
Catalyst: bis- (dimethylamino ethyl) ethers 0.3, N, 1.2 parts of N- dimethyl cyclohexyl amine, 2- hydroxypropyl trimethyl first
0.5 part of acid ammonium salt；
Organic silicon surfactant: 1.5 parts of L-6866,1.0 parts of L-6884；
Water: 2.2 parts；
Pentane: 15 parts, including 5 parts of pentane, 5 parts of isopentane, 5 parts of pentamethylene；
Nucleating agent: 2.5 parts of perfluoro-2-methyl-2-amylene；
Component B: feed liquid temperature is 10 DEG C,
Butane: 2 parts of normal butane；
Polyisocyanates: unmodified polyisocyanates, M20S, 37 parts；Modified polyisocyanate, NCO mass fraction are
24%, 130 parts.
40 DEG C of mould temperature, demoulding time 8min.
Embodiment 3
Component A: feed liquid temperature is 34 DEG C,
Glycol composition: hydroxyl value 550mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 250~350mgKOH/g, 5 parts；
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 550~590mgKOH/g, 80 parts；
Polyether polyol B: pentaerythrite polyether polyol, hydroxyl value be 480~580mgKOH/g, 15 parts；
Catalyst: bis- 0.3 parts of (dimethylamino ethyl) ether, 0.3 part of triethylenediamine；(the dimethylamino third of 1,3,5- tri-
Base) 0.4 part of-Hexahydrotriazine；
Organic silicon surfactant: 1.0 parts of L-6884,1.0 parts of L-6866；1.0 parts of AK8818；
Water: 1.0 parts；
Pentane: 10 parts of isopentane；
Nucleating agent: 1 part of ethylether of octafluoro amyl tetrafluoro；
Component B: feed liquid temperature is 8 DEG C,
Butane: 8 parts, including 6 parts of iso-butane, 2 parts of normal butane；
Polyisocyanates: unmodified polyisocyanates, MR200,90 parts；Modified polyisocyanate, NCO mass fraction are
28%, 72 parts.
42 DEG C of mould temperature, demoulding time 7min.
Embodiment 4
Component A: feed liquid temperature is 25 DEG C,
Pluronic polyols: hydroxyl value 400mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 100~300mgKOH/g, 20 parts；
Polyether polyol A: mannitol polyether polyol, hydroxyl value be 420~480mgKOH/g, 50 parts；
Polyether polyol B: phenylenediamine polyether polyol, hydroxyl value be 420~460mgKOH/g, 20 parts；
Polyether polyol C: pentaerythrite polyalcohol, hydroxyl value be 430~460mgKOH/g, 10 parts；
Catalyst: 0.5 part of tetramethylethylenediamine, N, 0.8 part of N- dimethyl cyclohexyl amine, 0.8 part of triethanolamine, 2,4,6- tri-
0.9 part of (dimethylaminomethyl) phenol；
Organic silicon surfactant: 1.0 parts of AK8805；
Water: 1.2 parts；
Pentane: 9 parts of pentamethylene；
Nucleating agent: four 2.8 parts of fluoro ethyl tetrafluoro propyl ethers；
Component B: feed liquid temperature is 12 DEG C,
Butane: 8 parts, including 5 parts of normal butane, 3 parts of iso-butane；
Polyisocyanates: unmodified polyisocyanates, PAPI27,100 parts；Modified polyisocyanate, NCO mass fraction are
16%, 40 parts.
45 DEG C of mould temperature, demoulding time 6min.
Embodiment 5
Component A: feed liquid temperature is 24 DEG C,
Pluronic polyols: hydroxyl value 350mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 250~350mgKOH/g, 50 parts；
Polyester polyol: benzoic anhydride polyester polyol, hydroxyl value be 340~440mgKOH/g, 50 parts；
Catalyst: 0.4 part of five methyl diethylentriamine, N, 1.0 parts of N- dimethyl benzylamine, N, N- dimethylethanolamine
0.6 part, 2,4,6- tri- 1.5 parts of (dimethylaminomethyl) phenol；
Organic silicon surfactant: 2.0 parts of L-6900,1.5 parts of AK8806；
Water: 1.4 parts；
Pentane: 12 parts, including 6 parts of pentamethylene, 6 parts of isopentane；
Nucleating agent: 0.5 part of difluoromethyl trifluoroethyl ether；
Component B: feed liquid temperature is 15 DEG C,
Butane: 4 parts；
Polyisocyanates: unmodified polyisocyanates, PAPI135,95 parts；Modified polyisocyanate, NCO mass fraction are
21%, 30 parts.
47 DEG C of mould temperature, demoulding time 5min.
Embodiment 6
Component A: feed liquid temperature is 28 DEG C,
Pluronic polyols: hydroxyl value 430mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 250~350mgKOH/g, 15 parts；
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 430~480mgKOH/g, 60 parts；
Polyether polyol B: phenylenediamine polyether polyol, hydroxyl value be 420~460mgKOH/g, 25 parts；
Catalyst: 1.8 parts of N, N- dimethylethanolamine, N, 1.4 parts of N- dimethyl benzylamine, 2- hydroxypropyl trimethyl octanoic acid
0.8 part of ammonium；
Organic silicon surfactant: 1.0 parts of L-6866,1.0 parts of L-6884,1.0 parts of L-6920,1.5 parts of AK8811；
Water: 1.7 parts；
Pentane: 13 parts, including 10 parts of pentane, 3 parts of isopentane；
Component B: feed liquid temperature is 18 DEG C,
Butane: 3 parts of iso-butane；
Polyisocyanates: unmodified polyisocyanates, 44V-40L, 90 parts；Modified polyisocyanate, NCO mass fraction are
21%, 57 parts.
50 DEG C of mould temperature, demoulding time 4min.
Embodiment 7
Component A: feed liquid temperature is 22 DEG C,
Pluronic polyols: hydroxyl value 410mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 220~250mgKOH/g, 10 parts；
Polyether polyol: sorbeth polyalcohol, hydroxyl value be 380~440mgKOH/g, 65 parts；
Plant oil polyether glycol: hydroxyl value be 520~600mgKOH/g, 10 parts；
Manny phase polyalcohol: hydroxyl value be 380~480mgKOH/g, 15 parts；
Catalyst: 1.2 parts of N, N- dimethyl cyclohexyl amine, N, 1.5 parts of N- dimethyl benzylamine, 1.3 parts of triethanolamine, 2- hydroxyl
1.0 parts of oxypropyl trimethyl ammonium formate；
Organic silicon surfactant: 2.0 parts of L-6866,1.0 parts of L-6920,2.0 parts of AK8863；
Water: 1.8 parts；
Pentane: 9 parts of pentane；
Nucleating agent: 1.5 parts, including 1 part of nine fluorine isobutyl ethyl ethers, 0.5 part of tetrafluoro ethyl-methyl ether；
Component B: feed liquid temperature is 12 DEG C,
Butane: 6 parts of normal butane；
Polyisocyanates: modified polyisocyanate, NCO mass fraction be 30%, 137 parts.
45 DEG C of mould temperature, demoulding time 5min.
Embodiment 8
Component A: feed liquid temperature is 26 DEG C,
Pluronic polyols: hydroxyl value 460mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 220~250mgKOH/g, 15 parts；
Polyether polyol: Sucrose polyethers polyalcohol, hydroxyl value be 460~580mgKOH/g, 65 parts；
Manny phase polyalcohol: hydroxyl value be 380~480mgKOH/g, 20 parts；
Catalyst: 0.2 part of five methyl diethylentriamine, 0.6 part, N of N- methyldicyclohexyl amine, N- dimethyl benzylamine
1.0 parts, 2,4,6- tri- 1.0 parts of (dimethylaminomethyl) phenol；
Organic silicon surfactant: 1.6 parts of AK8805,0.8 part of AK8810；
Water: 2.5 parts；
Pentane: 5 parts, including 3 parts of pentane, 2 parts of pentamethylene；
Nucleating agent: 2.5 parts, including 1.5 parts of hexafluoro propyl methyl ether, 1 part of perfluorobutadiene；
Component B: feed liquid temperature is 14 DEG C,
Butane: 12 parts, including 10 parts of normal butane, 2 parts of iso-butane；
Polyisocyanates: unmodified polyisocyanates, 2085,80 parts of Suprasec；Modified polyisocyanate, NCO mass
Score is 18%, 130 parts.
46 DEG C of mould temperature, demoulding time 5min.
Embodiment 9
Component A: feed liquid temperature is 23 DEG C,
Pluronic polyols: hydroxyl value 380mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 220~250mgKOH/g, 30 parts；
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 420~480mgKOH/g, 60 parts；
Polyester polyol: benzoic anhydride polyester polyol, hydroxyl value be 340~400mgKOH/g, 10 parts；
Catalyst: 0.4 part of tetramethylethylenediamine, N, 0.6 part of N- dimethylethanolamine, N, 1.1 parts of N- dimethyl benzylamine, 1,
0.5 part of 2- methylimidazole, 0.6 part of 2- hydroxypropyl trimethyl ammonium formate；
Organic silicon surfactant: 0.8 part of L-6920,1.0 parts of AK8805,1.0 parts of AK8818；
Water: 1.5 parts；
Pentane: 4 parts, including 2 parts of pentane, 2 parts of isopentane；
Nucleating agent: 2 parts of nona-fluoro butyl group methyl ether；
Component B: feed liquid temperature is 10 DEG C,
Butane: 10 parts, including 2 parts of normal butane, 8 parts of iso-butane；
Polyisocyanates: unmodified polyisocyanates, MR100,90 parts；Modified polyisocyanate, NCO mass fraction are
26%, 36 parts.
45 DEG C of mould temperature, demoulding time 5min.
Embodiment 10
Component A: feed liquid temperature is 25 DEG C,
Pluronic polyols: hydroxyl value 430mgKOH/g, 100 parts, comprising:
Polycarbonate polyol: hydroxyl value be 250~350mgKOH/g, 20 parts；
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 430~550mgKOH/g, 60 parts；
Polyether polyol B: phenylenediamine polyether polyol, hydroxyl value be 340~440mgKOH/g, 20 parts；
Catalyst: 0.4 part of five methyl diethylentriamine, N, 0.9 part of N- dimethyl cyclohexyl amine, 2,4,6- tri- (dimethyl
Amino methyl) 1.2 parts of phenol；
Organic silicon surfactant: 1.5 parts of AK8805,0.5 part of AK8806；
Water: 2 parts；
Pentane: 10 parts of pentamethylene；
Nucleating agent: perfluor -1- heptene, 3 parts；
Component B: feed liquid temperature is 12 DEG C,
Butane: 6 parts of iso-butane；
Polyisocyanates: unmodified polyisocyanates, M20S, 85 parts；Modified polyisocyanate, NCO mass fraction are
23%, 75 parts.
45 DEG C of mould temperature, demoulding time 5min.
The pure CP foaming of comparative example 1:()
Component A: feed liquid temperature is 25 DEG C,
Pluronic polyols: hydroxyl value 430mgKOH/g, 100 parts, comprising:
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 430~550mgKOH/g, 50 parts；
Polyether polyol B: phenylenediamine polyether polyol, hydroxyl value be 340~440mgKOH/g, 20 parts；
Polyether polyol C: glycerin polyether polyalcohol, hydroxyl value be 340~400mgKOH/g, 30 parts；
Catalyst: 0.4 part of five methyl diethylentriamine, N, 0.9 part of N- dimethyl cyclohexyl amine, 2,4,6- tri- (dimethyl
Amino methyl) 1.2 parts of phenol；
Organic silicon surfactant: 1.5 parts of AK8805,0.5 part of AK8806；
Water: 2.0 parts；
Pentane: 14 parts of pentamethylene；
Component B: feed liquid temperature is 25 DEG C,
Polyisocyanates: unmodified polyisocyanates, M20S, 140 parts.
45 DEG C of mould temperature, demoulding time 5min.
The pure butane foaming of comparative example 2:()
Component A: feed liquid temperature is 25 DEG C,
Pluronic polyols: hydroxyl value 430mgKOH/g, 100 parts, comprising:
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 430~490mgKOH/g, 50 parts；
Polyether polyol B: phenylenediamine polyether polyol, hydroxyl value be 340~440mgKOH/g, 20 parts；
Polyether polyol C: glycerin polyether polyalcohol, hydroxyl value be 340~400mgKOH/g, 30 parts；
Catalyst: 0.4 part of five methyl diethylentriamine, N, 0.9 part of N- dimethyl cyclohexyl amine, 2,4,6- tri- (dimethyl
Amino methyl) 1.2 parts of phenol；
Organic silicon surfactant: 1.5 parts of AK8805,0.5 part of AK8806；
Water: 2.2 parts；
Butane: 11 parts of iso-butane；
Component B: feed liquid temperature is 25 DEG C,
Polyisocyanates: unmodified polyisocyanates, M20S, 144 parts.
45 DEG C of mould temperature, demoulding time 5min.
Comparative example 3:(pentane and butane are mixed into component A simultaneously to foam)
Component A: feed liquid temperature is 25 DEG C,
Pluronic polyols: hydroxyl value 430mgKOH/g, 100 parts, comprising:
Polyether polyol A: Sucrose polyethers polyalcohol, hydroxyl value be 430~490mgKOH/g, 50 parts；
Polyether polyol B: phenylenediamine polyether polyol, hydroxyl value be 340~440mgKOH/g, 20 parts；
Polyether polyol C: glycerin polyether polyalcohol, hydroxyl value be 340~400mgKOH/g, 30 parts；
Catalyst: 0.4 part of five methyl diethylentriamine, N, 0.9 part of N- dimethyl cyclohexyl amine, 2,4,6- tri- (dimethyl
Amino methyl) 1.2 parts of phenol；
Organic silicon surfactant: 1.5 parts of AK8805,0.5 part of AK8806；
Water: 2.0 parts；
Pentane: 8 parts of pentamethylene；
Butane: 5 parts of iso-butane；
Component B: feed liquid temperature is 25 DEG C,
Polyisocyanates: unmodified polyisocyanates, M20S, 140 parts.
45 DEG C of mould temperature, demoulding time 5min.
The raw material of embodiment and comparative example and detection data are included in Tables 1 and 2 below.
1 embodiment 1-7 raw material proportioning of table and foaming properties
2 embodiment 8~10 of table and 1~3 raw material proportioning of comparative example and foaming properties
It is from above-mentioned Tables 1 and 2 it is found that smaller using the hard polyurethane foams thermal coefficient of the technology of the present invention preparation, absolutely
More preferably, high/low temperature size distortion rate is lower for hot property, foam good mechanical properties.And table 2 shows compared with comparative example 1~3,
The core density of foam is greatly lowered when just filling in embodiment 10, but compressive strength is close, high/low temperature dimensional stability more preferably,
Thermal coefficient is decreased obviously, excellent combination property.As it can be seen that extremely-low density hard polyurethane foams core density of the invention can be down to
About 26.0kg/m3, raw material groundwater increment is substantially reduced, but be still able to maintain good comprehensive performance, meets the needs of refrigerator manufacturer.
Technical solution of the present invention can be obviously improved the application performance of foam, therefore, under same process parameter, using of the invention
Technical solution can effectively reduce raw material groundwater increment, foam density be reduced, to reduce production cost.
Claims (8)
1. a kind of hard polyurethane foams of extremely-low density are respectively pre-mixed uniformly by component A and component B, then by component A and
Component B is uniform through mechanical mixture, foaming is prepared；Wherein, by weight,
Component A includes:
(1) Pluronic polyols, 100 parts, including: 3~50 parts of polycarbonate polyol；
(2) pentane, 4~15 parts；
(3) catalyst, 1~5 part；
(4) organic silicon surfactant, 1~5 part；
(5) water, 1~2.5 part；
(6) nucleating agent, 0~3 part；
Combining B includes:
(1) butane, 2~12 parts；
(2) polyisocyanates, 120~210 parts；
Above-mentioned each raw material is on the basis of 100 parts of Pluronic polyols.
2. hard polyurethane foams as described in claim 1, which is characterized in that the Pluronic polyols hydroxyl value be 250~
550mg KOH/g is based on 100 parts by Pluronic polyols parts by weight, and the Pluronic polyols includes:
Hydroxyl value is 3~50 parts of polycarbonate polyol of 100~350mg KOH/g, and hydroxyl value is the poly- of 120~600mg KOH/g
0~97 part of ethoxylated polyhydric alcohol, hydroxyl value is 0~50 part of polyester polyol of 100~450mg KOH/g, and hydroxyl value is 350~650mg
0~20 part of the vegetable oil polyol of KOH/g, hydroxyl value are 0~20 part of the Manny phase polyalcohol of 300~600mg KOH/g.
3. hard polyurethane foams as described in claim 1, which is characterized in that the pentane be selected from pentamethylene, pentane and
At least one of isopentane.
4. hard polyurethane foams as described in claim 1, which is characterized in that the nucleating agent is perfluoroolefine and/or contains
Fluorine ether, in which:
Perfluoroolefine is selected from perfluor -1- butylene, perfluor -2- butylene, perfluorobutadiene, perfluoro-2-methyl-2-amylene, perfluor -4-
At least one of methyl -2- amylene, octafluoro cyclopentene or perfluor -1- heptene；
Fluorine-containing ether be selected from pentafluoropropyl group methyl ether, hexafluoro propyl methyl ether, hexafluoro isopropyl methyl ether, nona-fluoro butyl group methyl ether,
Nine fluorine isobutyl methyl ethers, nona-fluoro butyl group ethylether, nine fluorine isobutyl ethyl ethers, bis-fluoro ethyls trifluoromethyl ethers, trifluoroethyl
Methyl ether, bis-fluoro ethyls tetrafluoro ethylether, difluoromethyl trifluoroethyl ether, bis- (trifluoroethyl) ethers, tetrafluoro ethyl-methyl ether, four
Fluoro ethyl ethylether, tetrafluoro ethyl propyl ether, four fluoro ethyl trifluoroethyl ethers, four fluoro ethyl tetrafluoro propyl ethers or octafluoro amyl four
At least one of fluoro ethyl ether.
5. hard polyurethane foams as described in claim 1, which is characterized in that the butane is in normal butane and iso-butane
At least one.
6. hard polyurethane foams as described in claim 1, which is characterized in that the polyisocyanates is unmodified polyisocyanate cyanogen
The mixture of the unmodified polyisocyanates and modified polyisocyanate of acid esters or modified polyisocyanate or arbitrary proportion.
7. hard polyurethane foams as claimed in claim 4, which is characterized in that the isocyanates of the modified polyisocyanate
The mass fraction of base is 16.0%~30.0%.
8. the preparation method of hard polyurethane foams described in claim 1, which comprises the following steps:
(1) it configures component A: in proportion adding Pluronic polyols, pentane, catalyst, organic silicon surfactant, water and nucleating agent
Enter into mixing kettle, stir evenly, obtain component A, material temperature control is 22~34 DEG C；
(2) it configures component B: butane, polyisocyanates being delivered to mixer in proportion, be uniformly mixed, obtain component B, material temperature control
It is made as 6~18 DEG C；
(3) hybrid injection: component A and component B are passed through in proportion in high pressure machine gun head mixed injection closed mold, sufficiently anti-
It answers, die temperance control is 35~50 DEG C, and product can be prepared by hard polyurethane foams after demoulding.
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