CN1237089C - Hard polyurethane foam composite and low temperature heat preserving insulation material made therefrom - Google Patents
Hard polyurethane foam composite and low temperature heat preserving insulation material made therefrom Download PDFInfo
- Publication number
- CN1237089C CN1237089C CNB031329853A CN03132985A CN1237089C CN 1237089 C CN1237089 C CN 1237089C CN B031329853 A CNB031329853 A CN B031329853A CN 03132985 A CN03132985 A CN 03132985A CN 1237089 C CN1237089 C CN 1237089C
- Authority
- CN
- China
- Prior art keywords
- weight
- synthetics
- hard polyurethane
- polyurethane foam
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
-
- 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
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
-
- 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
- C08J9/127—Mixtures of organic and inorganic blowing agents
-
- 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
- C08J9/141—Hydrocarbons
-
- 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
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
Provided is a rigid polyurethane foam composition exhibiting excellent heat-insulating properties, flame retardancy and mechanical characteristics, and a low-temperature insulator using the same. The rigid polyurethane foam composition comprises a polymeric 4,4'-diphenylmethane diisocyanate, a polyol mixture comprising (a) 30-70 wt% of a polyether polyol obtained by addition-polymerization of propylene oxide and ethylene oxide to pentaerythritol, (b) 10-30 wt% of a polyether polyol obtained by addition-polymerization of ethylene oxide and propylene oxide to sucrose, (c) 10-40 wt% of a polyester polyol obtained by addition-polymerization of ethylene oxide and propylene oxide to phthalic anhydride and (d) 5-30 wt% of a polyether polyol obtained by addition-polymerization of ethylene oxide and propylene oxide to glycerine having a bromine-substituent, where the NCO/OH ratio is adjusted to 1.0-1.4, and a mixture of 0-4 pts. wt. of water and 2-15 pts. wt. of cyclopentane, each based on 100 pts. wt. of the polyol mixture, is contained as the blowing agent.
Description
Technical field
The present invention relates to a kind of hard polyurethane foams synthetics that can be made into thermal insulation material with good heat insulating ability, flame retardant resistance and mechanical characteristics, and the thermal insulation material made of this synthetics of a kind of usefulness.
Background technology
Generally speaking, the hard urethane foam is to have foam to generate agent for example under the situation of water, cfc, hydrogenated chloride fluorine carbon, fluorine hydrogenated carbon, carbonic acid gas, pentamethylene etc., prepared by vulcabond and polyvalent alcohol.In addition, also can add catalyzer, fire retardant, tensio-active agent and other additives on demand.
Widely used is tolylene diisocyanate (TDI) and 4,4 '-diphenylmethanediisocyanate, and preferably selecting average functionality for use is 2.5 or more polymerization 4,4 '-diphenylmethanediisocyanate.
As for polyvalent alcohol, it can be to belong to polyethers or polyester.Wherein the application of polyether glycol is comparatively general, because it has the low and water-disintegrable stable characteristics of viscosity, handle easily, and also less expensive.The advantage of polyester polyol is thermostability and tensile strength aspect, but shows low in hydrolysis resistance.Urethane more than 90% is to be prepared from by polyether glycol, and wherein polyether glycol is used for special purposes.
Low-molecular-weight glycol or diamines then can be used as chain extension agent or linking agent.
In the past, cfc was used widely, and was because its thermal conductivity is low and have very high stability in air.But,, replace it with hydrogenated chloride fluorine carbon, pentamethylene or water again recently because of cfc pollutes the environment.In fact, as the good heat-insulating property of thermal insulation materials such as polyurethane foam, be owing to adopted the whipping agent of low heat conductivity.Whipping agent has than air and the lower thermal conductivity of carbonic acid gas.As time goes on, whipping agent can come out from the urethane internal divergence, and its position can be occupied by high thermal conductivity air on every side.The result causes the thermal conductivity of urethane to rise, and heat-insulating property descends.
At present, hydrogenated chloride fluorine carbon is furtherd investigate, because it does not have destructiveness to ozonosphere, thermal conductivity is lower, so and in can be from the Polyurethane Diffusion to the air its insulating characteristics can keep for a long time.But because hydrogenated chloride fluorine carbon is not a kind of harmless material fully, so its use still is restricted.
Pentamethylene can not produce and for example ozonosphere be damaged and cause pollutions such as Global warming, thereby receives much concern yet.But, because pentamethylene has blast characteristics, cause its flame retardant resistance to descend, so be necessary that still further research is to improve the flame retardant resistance of pentamethylene.
The physical property that contains the hard polyurethane foams of pentamethylene can be represented with density function.When the density of hard polyurethane foams reduced, its thermal conductivity can reduce, thereby its flame retardant properties is improved.But its physical property such as ultimate compression strength etc. can variation.This just makes the heat insulating ability and the physical property that must improve hard polyurethane foams simultaneously is the comparison difficulty, but this two specific character all is necessary for the very low temperature thermal insulation material or be used for the very low temperature pipe box of liquify natural gas accumulator tanks.
For improving the physical property of polyurethane foam, can increase the density of polyurethane foam, or add glass fibre or filled with carbon fibers thing.All can increase its thermal conductivity but increase density and add weighting material, reduce its heat insulating ability.
Tin and amine all can be used as catalyzer.
Because the low flame retardant resistance of urethane needs to use fire retardant, typically uses halogen, phosphorus and mineral compound, and they can be grouped into response type and auxiliary type.
Most of hard polyurethane foams itself there is no flame retardant resistance, but but are used in the place that needs flame retardant resistance, as are used in the building structure or thermal insulation material that keeps very low temperature in the liquify natural gas accumulator tanks.Traditionally, polyurethane foam satisfies its flame retardant resistance and requires by adding fire retardant, but when making whipping agent with pentamethylene, does not allow to add separately fire retardant and satisfy the required flame retardant properties of polyurethane foam.
The foam beads that forms when bubbling is little and when even, made foamy heat insulating ability and mechanical characteristics just can improve.For this purpose, need to use Silicon surfactant as the foam beads stablizer.
Summary of the invention
At above-mentioned technical background, the inventor is to neither causing environmental pollution, having the thermal insulation material of good mechanical characteristics and heat-insulating property to carry out intensive research again, find the available mixture of forming by two kinds of polyether glycols, a kind of polyester polyol and a kind of bromine polyvalent alcohol, with polymerization 4,4 '-diphenylmethanediisocyanate, under the condition that the pentamethylene existence that can not cause environmental pollution is arranged, react, thereby generate a kind of foam with excellent flame retardancy, mechanical characteristics and insulating characteristics.
An object of the present invention is to provide a kind of polyurethane foam synthetics of environmental sound.
Another object of the present invention provides a kind of polyurethane foam synthetics that good mechanical characteristics and heat insulating ability are arranged.
Another object of the present invention provides a kind ofly has good flame retardant resistance, mechanical characteristics and heat insulating ability, and the thermal insulation material of environmental sound.
Above-mentioned purpose of the present invention can realize by a kind of hard polyurethane foams synthetics is provided.Comprise a kind of polymerization 4,4 '-diphenylmethanediisocyanate in the described hard polyurethane foams synthetics; A kind of polyol blends wherein comprises: (a) account for the polyether glycol of 30-70% weight, it is by forming to tetramethylolmethane adding propylene oxide and ethylene oxide polymerization; (b) account for the polyether glycol of 10-30% weight, it is by adding propylene oxide to sucrose and ethylene oxide polymerization forms; (c) account for the polyester polyol of 10-40% weight, it is by adding propylene oxide to Tetra hydro Phthalic anhydride and ethylene oxide polymerization forms; And the polyether glycol that (d) accounts for 5-30% weight, it is by forming to bromo glycerine adding propylene oxide and ethylene oxide polymerization; In this synthetics, the NCO/OH ratio is between 1.0-1.4; Also comprising a kind of whipping agent, is 100 parts of bases as the weight with polyol blends, comprises in the described whipping agent with the water of 0-4 part weight and the pentamethylene of 2-15 part weight.
Description of drawings
Fig. 1 is an electron microscopic structure photo that is used to illustrate the microtexture of hard polyurethane foams of the present invention.
Embodiment
Among the present invention, under the condition that whipping agent exists, make the polyurethane foam synthetics by vulcabond and polyol blends reaction.The polyvalent alcohol composition that uses among the present invention is a kind of polyol blends, wherein comprise two kinds of polyether glycols, a kind of be polyester polyol and a kind of be the bromine polyvalent alcohol.Specifically, the polyol blends that uses among the present invention comprises: (a) account for the polyether glycol of 30-70% weight, it is by forming to tetramethylolmethane adding propylene oxide and ethylene oxide polymerization; (b) account for the polyether glycol of 10-30% weight, it is by adding propylene oxide to sucrose and ethylene oxide polymerization forms; (c) account for the polyester polyol of 10-40% weight, it is by adding propylene oxide to Tetra hydro Phthalic anhydride and ethylene oxide polymerization forms; (d) account for the polyether glycol of 5-30% weight, it is by adding propylene oxide to bromo glycerine and ethylene oxide polymerization forms.In this polyol blends, the characteristic of every kind of polyvalent alcohol is consistent.But the polyvalent alcohol of high OH value and functionality has high mechanical strength, but can cause the polyurethane foam synthetics to break firmly and easily very much.On the other hand, have very high ductility by the polyurethane foam synthetics of the polyvalent alcohol of high OH value and functionality preparation, thereby be difficult for again breaking.But, use the polyvalent alcohol of medium OH value and functionality, only can obtain low intensive polyurethane foam synthetics, can not fully satisfy the requirement of very low temperature insulation.For preparation has high intensity, ductility and the elastic thermal insulation material that is applied to very low temperature insulation purposes, need the mixture of two or more polyvalent alcohols.For obtaining required intensity and ductility, this polyol blends needs an optimum mixture ratio example.The blending ratio of described polyvalent alcohol will be suitable for making the polyurethane foam that is used for the very low temperature insulation.
The preferable range of the average OH value of polyol blends is 340-470.If average OH value is lower than 340, in the manufacturing reaction meeting of required cross-linked polyurethane insufficient, thereby to physical strength and the bad influence of spatial stability generation.On the other hand,, then can cause crosslinking reaction too much, make the polyurethane foam hardening, alarm, thereby its thermal conductivity is increased, the heat-proof quality variation if average OH value surpasses 470.
For the polymerization 4 of working among the present invention, 4 '-diphenylmethanediisocyanate, preferably select for use the average functionality value be 2.5-3.1 and at room temperature be in a liquid state that is a kind of.Polymerization 4, the molecular structure of 4 '-diphenylmethanediisocyanate is shown in following equation 1:
Equation 1:
Wherein, the scope of vulcabond is calculated by average N CO%, is preferably between the 29-32.NCO% is lower than at 29 o'clock, and its flowability is relatively poor; NCO% was greater than 32 o'clock, and its dimensional stability can degenerate under cold condition.
For the polymerization 4 that is aggregated in this synthetics, 4 '-diphenylmethanediisocyanate and polyol blends, its NCO/OH ratio is preferably between the 1.0-1.4.If the NCO/OH ratio, then generates the reaction of polyurethane foam less than 1.0 and does not finish and will stop.When the NCO/OH ratio between 1.0-1.4, that is to say, 4, when 4 '-diphenylmethanediisocyanate is slightly more, generate urethane after remaining compound can in addition reaction, generate biuret or allophanate, thereby the physical property of raising polymkeric substance.And, adding under the situation of catalyzer, have more 4,4 '-diphenylmethanediisocyanate can generate the poly-chlorinated isocyanurates of trimer, thereby improves flame retardant resistance.But if the NCO/OH ratio surpasses 1.4, the hard polyurethane foams synthetics can show relatively poor dimensional stability, and its rigidity uprises, and can produce the bristle thorn.
Pentamethylene not be preferably whipping agent because of can produce not polluting environment, and it is preferably to be used in combination with water.Among the present invention, be 100 parts of bases, use the water of 0-4 part weight and the pentamethylene of 2-15 part weight as weight with polyol blends.The density of the hard polyurethane foams that generates under this condition is 30-140Kg/m
3(kilograms per cubic meter).By the dosage of control whipping agent, also can with the density of hard polyurethane foams adjust to less than 30Kg/m
3Or greater than 140Kg/m
3
Behind the water and di-isocyanate reaction as auxiliary blowing agent, can generate urea and discharge carbonic acid gas.This carbonic acid gas is used for bubbling in polyurethane foam.Simultaneously, the heat that reaction produces between water and the vulcabond is used to evaporate pentamethylene.
Weight with polyol blends is 100 parts of bases, if the weight of water above 7 parts, not only can produce excessive reaction heat and burn phenomenon in the polyurethane foam that generates, and excessive carbon dioxide also can make the thermal conductivity of polyurethane foam rise.
The low vaporization temperature of pentamethylene makes the preparation polyurethane foam become easy.Simultaneously, the low heat conductivity of pentamethylene helps the formation of the high thermal insulation of polyurethane foam.And, pentamethylene with have nothing to do by problem of environmental pollutions such as damaging the ozone layer of causing of cfc (CFC) and hydrogenation cfc and Global warmings.Although pentamethylene decreases to the flame retardant resistance of thermal insulation material, can overcome this defective by using the bromine polyvalent alcohol.
Can use amine catalyst to accelerate the reaction of vulcabond and polyvalent alcohol.Among the present invention, catalyzer is selected from by pentamethyl-tetramethylene triamine, dimethyl cyclammonium, 3-ethane aminopropyl hexahydro-triamine, and the catalyzer group formed of their mixture.As the weight with polyol blends is 100 parts of bases, and the weight of catalyzer is preferably 0.1-2.0 part.If use catalyzer very few, then speed of reaction is understood slack-off and is generated incomplete polyurethane foam, and the physical property of this polyurethane foam is relatively poor; On the other hand,, then too fast speed of response can be occurred, in foam, crack and deflation can be produced if the amount of catalyzer surpasses 2.0 parts.
Whipping agent can evaporate because of the heat that produces in vulcabond and the polyol reaction process, thereby forms bubble in polyurethane foam.When the bubble bubble bigger, can make the physical strength and the heat insulating ability variation of polyurethane foam owing to internal pressure is accumulated into.
Polyurethane foam is to be combined by small-particle, is gathered into bigger particle because of surface tension between a plurality of small-particles.But macrobead can destroy the foamy physical property.Therefore, need in polyurethane foam, form little and homogeneous granules, to improve its physical property.In this, Silicon surfactant can play an important role.It makes the foam beads surface be with electric charge, can avoid them to get together together because of static repels mutually thereby make between each particle.The result can form little in polyurethane foam and homogeneous granules.
Preferred Silicon surfactant is a polyether siloxane, is 100 parts of bases as the weight with polyol blends, and the preferred weight of this Silicon surfactant is 0-3.0 part.If surpass 3.0 parts, then the physical strength of polyurethane foam can variation.
For making polyurethane foam have flame retardant resistance, need to add fire retardant.Spendable have a phosphorus fire retardant, and for example Tritolyl Phosphate is 100 parts of bases as the weight with polyol blends, and the weight of this phosphorus fire retardant is preferably 5-15 part.If the weight of fire retardant is less than 5 parts, satisfied flame retardant resistance will be can not get; If the weight of fire retardant surpasses 15 parts, its flame retardant resistance only can improve a little, but productivity can reduce.
Utilize polyurethane foam synthetics of the present invention, can prepare the thermal insulation material that is used for the low temperature insulation by technique known with good heat insulating ability, flame retardant resistance and mechanical characteristics.
By the following embodiment that is used for example, can better understanding be arranged to the present invention, but the present invention is not limited to embodiment.
Embodiment
Make polyurethane foam by composition listed in the following table 1.The catalyzer that uses in the present embodiment, fire retardant and tensio-active agent provide in table 2.
The component and the dosage of table 1 polyurethane foam synthetics
| Component | Embodiment | ||
| 1 | 2 | 3 | |
| Polyvalent alcohol 1 | 50.0 | 50.0 | 60.0 |
| Polyvalent alcohol 2 | 15.0 | 20.0 | 15.0 |
| Polyvalent alcohol 3 | 20.0 | 15.0 | 10.0 |
| Polyvalent alcohol 4 | 15.0 | 15.0 | 15.0 |
| Tensio-active agent | 1.5 | 1.3 | 1.5 |
| Catalyst A | 0.3 | 0.2 | 0.1 |
| Catalyst B | 0.7 | 0.4 | 0.3 |
| Fire retardant | 10.0 | 7.0 | 5.0 |
| Water | 0.7 | 0.4 | 0.3 |
| Pentamethylene | 7.0 | 4.7 | 3.7 |
| 4,4 '-diphenylmethanediisocyanate | 134.0 | 128.4 | 140.4 |
Wherein, polyvalent alcohol 1 is to be formed by tetramethylolmethane and propylene oxide/ethylene oxide polymerization;
Polyvalent alcohol 2 is to be formed by sucrose and propylene oxide/ethylene oxide polymerization;
Polyvalent alcohol 3 is to be formed by Tetra hydro Phthalic anhydride and propylene oxide/ethylene oxide polymerization;
Polyvalent alcohol 4 is to be formed by bromo glycerine and propylene oxide/ethylene oxide polymerization.
Table 2 catalyzer and additive
| Catalyst A | Pentamethyl-tetramethylene triamine (Pentamethyliethylene triamine) |
| Catalyst B | Dimethyl cyclammonium (Dimethylcyclohexylamine) |
| Catalyzer C | 3-ethane aminopropyl hexahydro-triamine (Tris (3-dimethylamino) propylhexahydrotriamine) |
| Catalyzer D | Triethylenediamine |
| Tensio-active agent | Polyether siloxane |
| Fire retardant | Tritolyl Phosphate |
The physical property of the hard polyurethane foams of preparation among the embodiment 1 to 3 is measured the result such as the following table 3 of gained.
The physical property of table 3 hard polyurethane foams
| Characteristic | Examination criteria | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (Kg/m 3) | ASTM D1622 | 50 | 84 | 113 |
| Thermal conductivity (kcal/m.h. ℃) | ASTM C518 | 0.0184 | 0.0196 | 0.0218 |
| Ultimate compression strength (kgf/cm 2) | ASTM D1621 | 4.01 | 8.69 | 13.68 |
| Tensile strength (kgf/cm 2) | ASTM D1623 | 4.63 | 7.31 | 10.14 |
| Flexural strength (kgf/cm 2) | KS M3830 | 5.61 | 9.78 | 16.76 |
| Flame retardant resistance | ASTM D4986 | Spontaneous combustion | Spontaneous combustion | Spontaneous combustion |
Under electron microscope, can be observed the microtexture of the polyurethane foam of preparation among the embodiment 1.This foam is the particle that forms when bubbling based on polymer.As can be seen from Figure 1, the polyurethane foam among the present invention comprises little and homogeneous granules.
Even there is the pentamethylene of aforementioned environmentally safe, polyurethane foam also can obtain good mechanical characteristics energy, and for example ultimate compression strength keeps its good heat-insulating property simultaneously.
Invention has been described in the mode of example in the front, is understandable that wherein the term of Cai Yonging is for convenience of description, rather than limitation of the invention.According to above-mentioned instruction, can carry out various modifications or variation to the present invention.Therefore, within the scope of the claims, the present invention can also be by the embodied in other outside the description of front.
Claims (8)
1, a kind of hard polyurethane foams synthetics wherein comprises:
A kind of polymerization 4,4 '-diphenylmethanediisocyanate;
A kind of polyol blends wherein comprises: (a) account for the polyether glycol of 30-70% weight, it is by forming to tetramethylolmethane addition propylene oxide and ethylene oxide polymerization; (b) account for the polyether glycol of 10-30% weight, it is by forming to sucrose addition propylene oxide and ethylene oxide polymerization; (c) account for the polyester polyol of 10-40% weight, it is by forming to Tetra hydro Phthalic anhydride addition propylene oxide and ethylene oxide polymerization; And the polyether glycol that (d) accounts for 5-30% weight, it is by forming to bromo glycerine addition propylene oxide and ethylene oxide polymerization; The average OH value of described polyol blends is between 340-470, and in this synthetics, the NCO/OH ratio is between 1.0-1.4;
Also comprising a kind of whipping agent, is 100 parts of bases as the weight with polyol blends, comprises in the described whipping agent with the water of 0-4 part weight and the pentamethylene of 2-15 part weight.
2, hard polyurethane foams synthetics according to claim 1 is characterized in that, and is described 4, and the functionality of 4 '-diphenylmethanediisocyanate is 2.5-3.1.
3, hard polyurethane foams synthetics according to claim 1 and 2 is characterized in that, also comprises phosphorus fire retardant, is 100 parts of bases as the weight with polyol blends, and the weight of described phosphorus fire retardant is 5-20 part.
4, hard polyurethane foams synthetics according to claim 1 and 2 is characterized in that, also comprises amine catalyst, is 100 parts of bases as the weight with polyol blends, and the weight of described amine catalyst is 0-2.0 part.
5, hard polyurethane foams synthetics according to claim 1 and 2 is characterized in that, also comprises Silicon surfactant, is 100 parts of bases as the weight with polyol blends, and the weight of described Silicon surfactant is 0-3.0 part.
6, hard polyurethane foams synthetics according to claim 3 is characterized in that, described phosphorus fire retardant is a Tritolyl Phosphate.
7, hard polyurethane foams synthetics according to claim 5 is characterized in that, described Silicon surfactant is a polyether siloxane.
8, a kind of thermal insulation material is characterized in that, described thermal insulation material is to be prepared from by the described polyurethane foam synthetics of claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0017125 | 2003-03-19 | ||
| KR1020030017125 | 2003-03-19 | ||
| KR10-2003-0017125A KR100507847B1 (en) | 2003-03-19 | 2003-03-19 | Hard polyurethane foam composition and insulation for keeping coolness using it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1532214A CN1532214A (en) | 2004-09-29 |
| CN1237089C true CN1237089C (en) | 2006-01-18 |
Family
ID=33297294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031329853A Expired - Lifetime CN1237089C (en) | 2003-03-19 | 2003-07-23 | Hard polyurethane foam composite and low temperature heat preserving insulation material made therefrom |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2004285321A (en) |
| KR (1) | KR100507847B1 (en) |
| CN (1) | CN1237089C (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100738140B1 (en) * | 2005-11-09 | 2007-07-10 | 현대자동차주식회사 | Polyurethane Foam, which has been used in Automotive Interior Parts, improved in Mechanical Properties |
| CN100424122C (en) * | 2006-08-23 | 2008-10-08 | 杨彦威 | Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene |
| JP2008074880A (en) * | 2006-09-19 | 2008-04-03 | Nippon Polyurethane Ind Co Ltd | Method for producing rigid polyurethane slab foam, rigid polyurethane slab foam and insulating material for piping |
| JP2008133317A (en) * | 2006-11-27 | 2008-06-12 | Toyo Tire & Rubber Co Ltd | Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam |
| WO2010066635A1 (en) * | 2008-12-10 | 2010-06-17 | Basf Se | Water-blown rigid foams with improved mechanical properties at low temperatures |
| JP5546785B2 (en) * | 2009-03-25 | 2014-07-09 | アキレス株式会社 | Rigid polyurethane foam composition |
| JP5644116B2 (en) * | 2010-01-21 | 2014-12-24 | 株式会社ブリヂストン | High flame retardant polyurethane foam |
| JP5644189B2 (en) * | 2010-06-03 | 2014-12-24 | 株式会社ブリヂストン | High flame retardant polyurethane foam |
| KR101306144B1 (en) * | 2011-06-13 | 2013-09-17 | (주)동성화인텍 | Water blowned polyurethane composition for earth-based lng tank and manufacturing method of it |
| RU2640798C2 (en) * | 2012-02-28 | 2018-01-12 | Басф Се | Method of producing hard polymeric foam materials |
| JP6155758B2 (en) | 2013-03-29 | 2017-07-05 | 株式会社Ihi | Cryogenic liquid tank |
| ITMI20131603A1 (en) * | 2013-09-30 | 2015-03-30 | Dow Global Technologies Llc | MIXTURES OF POLYOLS AND POLYESTER POLYOLS AND PREPARATION OF RIGID POLYURETHANE EXPANSIONS |
| CN103865023B (en) * | 2014-03-03 | 2016-01-13 | 晋江市闽高纺织科技有限公司 | Environment-protecting polyurethane injection material and preparation method thereof |
| CN104927023A (en) * | 2014-11-06 | 2015-09-23 | 上海世富环保节能科技股份有限公司 | High-performance hard-foam polyurethane heat insulating material for exterior walls |
| CN106243375A (en) * | 2016-08-03 | 2016-12-21 | 南宁可煜能源科技有限公司 | Floride-free type polyurethane insulation material |
| CA3049930A1 (en) * | 2017-01-25 | 2018-08-02 | Basf Se | Cold flexible polyurethane formulation |
| CN108164672A (en) * | 2017-12-28 | 2018-06-15 | 青岛海尔股份有限公司 | Polyurethane rigid foam plastic and preparation method thereof |
| CN108329448A (en) * | 2017-12-29 | 2018-07-27 | 山东益盛聚氨酯有限公司 | A kind of combined polyether, polyurethane raw material composition, hard polyurethane foam and its preparation and application |
| KR102248134B1 (en) | 2019-11-15 | 2021-05-04 | 미쓰이케미칼앤드에스케이씨폴리우레탄 주식회사 | Non-combustible foam and manufacturinng method thereof |
| CN114940005A (en) * | 2022-07-04 | 2022-08-26 | 张家港飞腾复合新材料股份有限公司 | High-heat-insulation heat-preservation composite board and production process thereof |
| CN117209715B (en) * | 2023-10-11 | 2024-02-27 | 山东宝泰隔热材料有限公司 | Use method of polyurethane sealing material |
-
2003
- 2003-03-19 KR KR10-2003-0017125A patent/KR100507847B1/en active IP Right Grant
- 2003-07-23 CN CNB031329853A patent/CN1237089C/en not_active Expired - Lifetime
- 2003-09-12 JP JP2003322081A patent/JP2004285321A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040082548A (en) | 2004-09-30 |
| CN1532214A (en) | 2004-09-29 |
| KR100507847B1 (en) | 2005-08-17 |
| JP2004285321A (en) | 2004-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1237089C (en) | Hard polyurethane foam composite and low temperature heat preserving insulation material made therefrom | |
| CN1237088C (en) | Hard polyurethane foam composite and low temperature heat preserving insulation material made therefrom | |
| CN1260809A (en) | Isocyanate compositions for foaming polyurethane plastic foams | |
| CN113637142B (en) | Spraying type flame-retardant polyurethane composite material and preparation method and use method thereof | |
| CN1045975C (en) | Rigid foamed polyurethane and process for manufacture of same | |
| CN1765949A (en) | Polyurethane foam and process for producing the same | |
| CN1662588A (en) | Polyurethane or polyisocyanurate foams blown with hydrofluorocarbons and carbon atoms | |
| CN1111553C (en) | The manufacture method of the urethane-rigid foam of hydrocarbon compound foaming | |
| CN1249115C (en) | Lowly air-permeable flexible polyurethane foam block and process for producing the same | |
| CN105384902B (en) | A kind of building heat preservation novel environment friendly flame retardant polyurethane material | |
| BR0115467B1 (en) | process for producing a low density rigid polyurethane foam, rigid polyurethane foam and thermal insulation board. | |
| JP3072560B2 (en) | Polyurethane foam for ultra-low temperature cooling and method for producing the same | |
| CN1045973C (en) | Process for the preparation of polyurethane resin and rigid polyurethane foam | |
| CN1175599A (en) | Polyisocyanate compositions | |
| CN1492900A (en) | Process for making polyurethane integral skin foams | |
| CN1213089C (en) | Hard polyurethane foam material and insulator | |
| CN1084347C (en) | Foamed thermal insulating and insulated structure | |
| KR100738140B1 (en) | Polyurethane Foam, which has been used in Automotive Interior Parts, improved in Mechanical Properties | |
| KR20040095426A (en) | A Rigid Polyurethane Foam Containing Calcium Carbonate | |
| CN1621429A (en) | Combined polyol for polyisocyanurate foam | |
| CN114133512B (en) | All-water foaming polyurethane raw material composition for polyurethane security door and preparation method thereof | |
| KR20040024064A (en) | Manufacture of polyisocyanurate foam blown by HFC family blowing agent and recycled polyol which obtained from polyurethane foam scrap | |
| Burgaz et al. | PU rigid composite foams containing micron-sized fillers | |
| CN1253483C (en) | Isocyanate compositions and their use in preparation of expanded polyurethane materials with endowed flame-resistance | |
| CN1184492A (en) | Rigid polyurethane foams |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060118 |
|
| CX01 | Expiry of patent term |