CN101516946A - Process for producing rigid polyurethane slab foam, rigid polyurethane slab foam, and heat-insulating material for piping - Google Patents

Process for producing rigid polyurethane slab foam, rigid polyurethane slab foam, and heat-insulating material for piping Download PDF

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CN101516946A
CN101516946A CNA2007800348728A CN200780034872A CN101516946A CN 101516946 A CN101516946 A CN 101516946A CN A2007800348728 A CNA2007800348728 A CN A2007800348728A CN 200780034872 A CN200780034872 A CN 200780034872A CN 101516946 A CN101516946 A CN 101516946A
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rigid polyurethane
slab foam
foam
mdi
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CN101516946B (en
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猪原英树
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Nippon Polyurethane Industry Co Ltd
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Nippon Polyurethane Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—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
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4275—Valcrolactone and/or substituted valcrolactone
    • 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
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a process for producing a rigid polyurethane slab foam which does not scorch inside, has a low thermal conductivity, retains excellent flame retardancy over long, and has excellent dimensional stability. A foam-forming composition comprising [A] a modified polyisocyanate which is obtained by modifying at least part of a polymeric MDI having an MDI content of 30-80 mass% with a modifier comprising a polyester polyol having a hydroxy value of 150-300 mg-KOH/g and which has an NCO content of 24.0-28.0%, [B] a polyol ingredient comprising at least 50 mass% at least one member selected among (B1) a polyether polyol made with toluenediamine as an initiator, (B2) a polyether polyol made with sorbitol as an initiator, and (B3) a polyether polyol made with sucrose as an initiator, and [C] a blowing agent comprising water is reacted to cause it to freely foam, with the top kept open.

Description

The manufacture method of rigid polyurethane slab foam, rigid polyurethane slab foam and heat-insulating material for piping
Technical field
The present invention relates to manufacture method, rigid polyurethane slab foam and the heat-insulating material for piping of rigid polyurethane slab foam (rigid polyurethane slabfoam).More particularly, the present invention relates to inner not take place that coking, thermal conductivity are low, the manufacture method of the rigid polyurethane slab foam of excellent in flame retardance rigid polyurethane slab foam of making by this method and the heat-insulating material for piping that this rigid polyurethane slab foam severing processing is obtained.
Rigid polyurethane slab foam of the present invention is not foaming and the slab foam that is shaped to the specified shape such as various panels, plate, refrigerator chamber, neither be as foam-in-place the slab foam of spray coating foaming, but hard " slab foam " by making the composition free foaming in the mould that is injected into the open-top state or preparing by the composition free foaming that makes on the continuous circuit that is ejected into the open-top state continuously.
Background technology
In the past, as the whipping agent that is used to form hard polyurethane foams, used chloro-fluoro-carbon kind, hydrofluorocarbon class.Yet, because nearest requirements such as free-floride make water receive publicity as the hard polyurethane foams of the water foaming formulation of whipping agent.
Be used for containing polyisocyanates, polyhydroxy reactant and as the water of whipping agent by the composition that the water foaming formulation forms hard polyurethane foams.Here, as " polyisocyanates ", use the poly methylene poly phenyl poly isocyanate that comprises diphenylmethanediisocyanate usually.In addition, as the part of " polyhydroxy reactant ", use on tolylene diamine addition of ethylene oxide, propylene oxide and the polyether glycol (for example, with reference to patent documentation 1～5) that forms.
Yet, comprise disclosed composition in the patent documentation 1～5, make under the situation of rigid polyurethane slab foam by the composition of known water foaming formulation in the past, have the problem that produces coking (incipient scorch) in the inside of formed slab foam.This is because in the formation of the slab foam of water foaming formulation, thermal value is big, and is the shape (plate) of wall thickness, so the inner heat reasons such as (inner heat storage capacity are big) that is difficult to leave.And, cause bad order, the intensity of the end article that the severing slab foam obtains bad etc. in the inner coking that takes place of slab foam.Like this, the inside coking that can not become special problem in the thin moulded foam (mold foam) of wall becomes serious problems when making slab foam, wish very much and can address this problem.
In addition, all have high thermal conductivity by the hard polyurethane foams of disclosed composition manufacturing in the patent documentation 1～5, and do not have sufficient insulation effect and heat insulation effect.In addition, can not satisfy flame retardant resistance and dimensional stability etc.
Patent documentation 1: Japanese kokai publication hei 5-186549 communique
Patent documentation 2: Japanese kokai publication hei 6-228260 communique
Patent documentation 3: Japanese kokai publication hei 6-239956 communique
Patent documentation 4: Japanese kokai publication hei 7-10955 communique
Patent documentation 5: Japanese kokai publication hei 9-132631 communique
Summary of the invention
The problem that invention will solve
The present invention is based on above situation and makes.First purpose of the present invention provide inner do not take place coking, thermal conductivity low, can through the time ground keep the also manufacture method of the rigid polyurethane slab foam of excellence of excellent flame and dimensional stability.Second purpose of the present invention provide inner do not take place coking, thermal conductivity low, can through the time ground keep the also rigid polyurethane slab foam of excellence of excellent flame and dimensional stability.The 3rd purpose of the present invention provides heat-insulating material for piping, this thermal insulation material obtains by severing processing rigid polyurethane slab foam, and bad order, the intensity that causes because of coking is bad etc., thermal conductivity is low and have sufficient insulation effect and heat insulation effect, can through the time keep excellent flame, also have excellent size stability.
The method that is used to deal with problems
Manufacture method of the present invention is characterised in that, allow foam form the property composition react, free foaming under the open-top state, wherein, this foam forms property composition and contains: [A] use by hydroxyl value be properties-correcting agent (following also be called " specific properties-correcting agent ") modification that the polyester polyol of 150～300mgKOH/g the constitutes poly methylene poly phenyl poly isocyanate (following also be called " polymeric MDI (a) ") that contains 30～80 quality % diphenylmethanediisocyanates (hereinafter to be referred as " MDI ") at least a portion obtained, NCO content is 24.0～28.0% modified polyisocyanate; [B] contain total amount be 50 quality % above to be selected from the tolylene diamine be the polyether glycol (B1) of initiator, be the polyether glycol (B2) of initiator with the Sorbitol Powder and be at least a polyhydroxy reactant in the polyether glycol (B3) of initiator with sucrose; And [C] whipping agent of constituting by water.
In manufacture method of the present invention, following embodiment is preferred.(1) hydroxyl value that is used to obtain the employed specific properties-correcting agent of aforementioned composition [A] is 200～300mgKOH/g, and the NCO content of this composition [A] is 24.5～27.5%.(2) specific properties-correcting agent is by being selected from ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, triethylene glycol and 3-methyl isophthalic acid, at least a polyvalent alcohol in the 5-pentanediol and the polyester polyol that is selected from least a polyprotonic acid acquisition in phthalic acid, m-phthalic acid, terephthalic acid and the hexanodioic acid.(3) specific properties-correcting agent is the polyester polyol that is obtained by Diethylene Glycol and phthalic acid and/or hexanodioic acid.(4) aforementioned composition [A] mixes with the remainder (a2) of polymeric MDI (a) after handling and obtains by with specific properties-correcting agent the part (a1) of polymeric MDI (a) being carried out modification.(5) part (a1) for the polymeric MDI of handling in modification (a) is MDI (two nucleome).(6) aforementioned composition [B] comprises polyether glycol (B1), polyether glycol (B2) and polyether glycol (B3).(7) polyether glycol (B1) obtains by oxyethane and/or propylene oxide are added on the tolylene diamine, and especially adding to the oxyethane on the tolylene diamine and the quality ratio ([EO]: [PO]) of propylene oxide is 0～50: 100～50.(8) polyether glycol (B2) obtains by oxyethane and/or propylene oxide are added on the Sorbitol Powder, and especially adding to the oxyethane on the Sorbitol Powder and the quality ratio ([EO]: [PO]) of propylene oxide is 0～50: 100～50.(9) polyether glycol (B 3) obtains by oxyethane and/or propylene oxide are added on the sucrose, and especially adding to the oxyethane on the sucrose and the quality ratio ([EO]: [PO]) of propylene oxide is 0～50: 100～50.
Rigid polyurethane slab foam of the present invention is characterised in that, obtains by manufacture method of the present invention.Rigid polyurethane slab foam of the present invention is preferably by having 0.25m with aforementioned foam formation property composition 2Free foaming forms in the mould of the open-top state of above floorage.In addition, rigid polyurethane slab foam of the present invention preferably will be ejected into aforementioned foam on the continuous circuit of open-top state continuously with the width more than the 0.5m and form property composition free foaming and form.
Heat-insulating material for piping of the present invention is characterised in that, processes rigid polyurethane slab foam of the present invention by severing and obtains.
The invention effect
Manufacturing method according to the invention, can be manufactured on intralamellar part do not take place coking, thermal conductivity low, through the time keep excellent flame and the also excellent rigid polyurethane slab foam of dimensional stability.Coking does not take place in rigid polyurethane slab foam of the present invention in inside, thermal conductivity is low, can through the time keep excellent flame, and dimensional stability is also excellent.Bad order, the intensity that heat-insulating material for piping of the present invention does not cause because of coking is bad etc., and thermal conductivity is low and have sufficient insulation effect and a heat insulation effect, can through the time ground keep excellent flame, and also excellence of dimensional stability.
Description of drawings
Fig. 1 shows the stereographic map of an example of heat-insulating material for piping of the present invention.
Fig. 2 is the explanatory view shown in the part that thermal insulation material shown in Figure 1 is installed in the state on the pipeline is cut.
Description of reference numerals
1A thermal insulation material 1B thermal insulation material 3 securing gears
Embodiment
Below describe the present invention in detail.
(manufacture method of the present invention)
Manufacture method of the present invention has following feature: allow foam form the property composition react, free foaming under the open-top state, wherein said foam form the property composition and contain: the composition [A] that comprises modified polyisocyanate; With total amount is that ratio more than the 50 quality % comprises at least a polyhydroxy reactant that is selected from polyether glycol (B1), polyether glycol (B2) and the polyether glycol (B3); Composition [C] by water (whipping agent) formation.
(composition [A])
Composition [A] is the modified polyisocyanate that at least a portion obtained that contains the polymeric MDI (a) of MDI (two nucleomes) with specific modifier modification.In the MDI (two nucleomes) that constitutes polymeric MDI (a), contain 4,4 '-MDI, 2,4 '-MDI, 2, the isomer of 2 '-MDI, 4, the ratio that 4 '-MDI accounts for MDI is preferably more than 50%.
The ratio that MDI (two nucleomes) accounts for polymeric MDI (a) is 30～80 quality %, is preferably 35～75 quality %.
When the ratio of MDI (two nucleomes) was lower than 30 quality %, the viscosity of the modified polyisocyanate that is obtained by this polymeric MDI became excessive, for bringing disadvantageous effect with the Combination of composition [B].On the other hand, when the ratio of MDI (two nucleomes) surpasses 80 quality %, contain the undercapacity of the composition of the modified polyisocyanate that is obtained by this polymeric MDI, foam can not normally erect, and can not form desired rigid polyurethane slab foam.In addition, the rigid polyurethane slab foam that is formed by said composition shows fragility, does not have full intensity.In addition, the storage stability of polymeric MDI (a), especially the liquid package stability under the low temperature atmosphere below 0 ℃ worsens (for example crystallization is separated out).
Composition [A] can obtain by at least a portion with specific modifier modification polymeric MDI (a).The specific properties-correcting agent that is used for modified poly MDI is made of the polyester polyol of hydroxyl value 150～300mgKOH/g.
The polyester polyol that constitutes specific properties-correcting agent can obtain by allow polyvalent alcohol and polyprotonic acid carry out esterification with ordinary method.
Here, as polyvalent alcohol, ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, triethylene glycol and 3-methyl isophthalic acid, 5-pentanediol are preferred, and Diethylene Glycol is particularly preferred.
In addition, as polyprotonic acid, phthalic acid, m-phthalic acid, terephthalic acid and hexanodioic acid are preferred, and phthalic acid and hexanodioic acid are particularly preferred.
As the suitable polyester polyol that constitutes specific properties-correcting agent, can enumerate polyester polyol by Diethylene Glycol and phthalic acid and/or hexanodioic acid acquisition.By using described polyester polyol as specific properties-correcting agent, the outward appearance of gained modified polyisocyanate good (muddiness of liquid does not take place), in addition, the gained rigid polyurethane slab foam through the time after combustionproperty, dimensional stability be excellent.
The hydroxyl value that constitutes the polyester polyol of specific properties-correcting agent is 150～300mgKOH/g, is preferably 200～300mgKOH/g, more preferably 230～270mgKOH/g.At the polyester polyol that uses hydroxyl value to be lower than 150mgKOH/g during as the properties-correcting agent of polymeric MDI, the intensity of the rigid polyurethane slab foam that is formed by resulting composition reduces, causing that thus dimensional stability descends, therefore is not preferred (with reference to comparative example 1 described later and comparative example 2).On the other hand, during as the properties-correcting agent of polymeric MDI, the gained modified polyisocyanate takes place muddy (with reference to preparation example 13 described later and preparation example 14) at the polyester polyol that uses hydroxyl value to surpass 300mgKOH/g.As time goes on be separated (the becoming uneven liquid) of liquid etc. taken place in this modified polyisocyanate, and therefore the storage stability variation is not preferred.
The functional group's number that constitutes the polyester polyol of specific properties-correcting agent is preferably 2～4, is preferably 2 especially.At the polyester (monohydroxy-alcohol) that uses simple function (functional group's number is 1) during as the properties-correcting agent of polymeric MDI (a), reductions such as the compressive strength of the rigid polyurethane slab foam that forms by resulting composition, dimensional stability.On the other hand, be polyester polyol 5 or more during using functional group's number as the properties-correcting agent of polymeric MDI (a), the viscosity of gained modified isocyanate becomes too high, for example, has caused rough sledding such as mixing is bad.
The number-average molecular weight that constitutes the polyester polyol of specific properties-correcting agent is preferably 370～750, and more preferably 370～550.
As method, can be set forth in the method for adding specific properties-correcting agent and in this system of heating, mixing in the polymeric MDI (a) of preheating with specific modifier modification.Heating temperature during stirring is 50～100 ℃ for example, is preferably 60～80 ℃.
The method of coming prepared composition [A] as " part " modification with polymeric MDI (a), for example can be listed below method: (1) is divided into a part (a1) and remainder (a2) with polymeric MDI (a), (2) handle " part of polymeric MDI (a1) " with specific modifier modification, obtain " (polymerization) MDI (A1) of modification ", (3) are with " (polymerization) MDI (A1) of modification " and " remainder of polymeric MDI (a2) " the blended method that does not have modification.By prepared composition [A] in this way, the viscosity that can suppress in the gained composition [A] raises.
Here, " part of polymeric MDI (a1) " that modification is handled needs not be identical composition with " remainder of polymeric MDI (a2) " that add the back, and for example, nucleome distribution separately etc. can be different.In addition, can prepare two kinds of different polymeric MDIs such as nucleome distribution respectively, wherein a kind of as composition (a1), another kind of as composition (a2).Here, from the viewpoints such as effect excellence that the viscosity that suppresses gained composition [A] raises, it is preferred that " part of polymeric MDI (a1) " that modification is handled only is made of MDI (two nucleomes).
In this case, (1) polymeric MDI (a) is divided for a part (a1) that constitutes by MDI and the remainder (a2) that constitutes by polymeric MDI (perhaps, prepare (a1) composition that constitutes by MDI and (a2) composition that constitutes by polymeric MDI respectively), (2) by handle " part (a1) that constitutes by MDI " with specific modifier modification, obtain " MDI of modification (A1) ", (3) " MDI of modification (A1) " mixed with " remainder of polymeric MDI (a2) ", obtain composition [A] thus.In this case, in " remainder of polymeric MDI (a2) ", also can comprise MDI (two nucleomes).
In addition, can unlike aforementioned, cut apart, " all " of polymeric MDI (a) be carried out modification handle.In addition, even under the situation of modified poly MDI (a) " all ", in " modified polyisocyanate " of the constituent of gained [A], the coexistence of the polymeric MDI molecule of unmodified polymeric MDI molecule and modification.That is to say that the molecule that the molecule that constitutes the polyether glycol of specific properties-correcting agent is not with all constitute polymeric MDIs (a) combines and forms prepolymer.
For example, using formula HO-R 1-OH (in the formula, R 1Be the group that contains polyester construction) in " modified polyisocyanate " of polyester polyol modification of expression, there is formula R 2(NCO) m(in the formula, R 2Be the polymethylene polyphenyl structural unit, m is the integer more than 2.) expression " unmodified polymeric MDI molecule " and formula (OCN) M-1R 2-NHCOO-R 1-O-CONH-R 2(NCO) M-1" the polymeric MDI molecule of modification " of expression.
The NCO content of the modified polyisocyanate of constituent [A] is generally 24.0～28.0%, is preferably 24.5～27.5%.Thus, thermal value reduces, and it is gentle that the reaction when foam forms becomes, even the slab foam of wall thickness also can positively prevent inner pyrogenic generation.The NCO content of modified polyisocyanate can be controlled by the consumption (with respect to the usage ratio of polymeric MDI (a)) of regulating specific properties-correcting agent.
NCO content is lower than 24.0% modified polyisocyanate because viscosity becomes excessive, can not be in the pipeline of foaming machine, the flexible pipe internal recycle, can not with the polyol blends uniform mixing that contains composition [B] (with reference to comparative example 7 described later).
On the other hand, the NCO content of modified polyisocyanate surpasses at 28.0% o'clock, in the slab foam that is formed by resulting composition, can not prevent the inner coking (with reference to comparative example 5 described later) that takes place.
(composition [B])
The composition [B] that constitutes foam formation property composition is made of polyhydroxy reactant, this polyhydroxy reactant comprises that to be selected from the tolylene diamine be the polyether glycol (B1) of initiator, be the polyether glycol (B2) of initiator with the Sorbitol Powder and be at least a in the polyether glycol (B3) of initiator with sucrose, preferred two kinds, more preferably three kinds, these total amount is more than the 50 quality %.
Polyether glycol (B1) by with tolylene diamine as initiator, and addition of ethylene oxide and/or propylene oxide obtain thereon.
The composition [B] of the polyether glycol (B1) by containing a certain proportion of tolylene diamine system in formed rigid polyurethane slab foam, can be sought the miniaturization of abscess, realizes low thermal conductivity (heat insulating ability and heat retaining property).In addition, can give excellent flame for formed rigid polyurethane slab foam.In addition, it also is excellent containing the composition [B] of polyether glycol (B1) and the consistency of composition [A].
As tolylene diamine, can be with 2,4-tolylene diamine, 2, the 6-tolylene diamine uses or uses the mixture of the two individually.
Here, the quality ratio of the oxyethane of addition and propylene oxide on tolylene diamine ([EO]: [PO]) is preferably 0～50: 100～50, and more preferably 0～35: 100～65.Thus, can improve the dimensional stability of gained rigid polyurethane slab foam.
The hydroxyl value of polyether glycol (B1) is preferably 200～700mgKOH/g, more preferably 300～500mgKOH/g.The number-average molecular weight of polyether glycol (B1) is preferably 320～1200, and more preferably 450～750.
Polyether glycol (B2) is by being initiator with Sorbitol Powder (sorbitol), and addition of ethylene oxide and/or propylene oxide obtain thereon.
Here, the quality ratio of the oxyethane of addition and propylene oxide ([EO]: [PO]) is preferably 0～50: 100～50 on Sorbitol Powder.
The hydroxyl value of polyether glycol (B2) is preferably 200～680mgKOH/g, more preferably 350～500mgKOH/g.The number-average molecular weight of polyether glycol (B2) is preferably 500～1700, and more preferably 670～1000.
Polyether glycol (B3) is by being initiator with sucrose, and addition of ethylene oxide and/or propylene oxide obtain thereon.
Here, the quality ratio of the oxyethane of addition and propylene oxide ([EO]: [PO]) is preferably 0～50: 100～50 on sucrose.
The hydroxyl value of polyether glycol (B3) is preferably 300～600mgKOH/g, more preferably 380～450mgKOH/g.The number-average molecular weight of polyether glycol (B3) is preferably 700～1500, and more preferably 1000～1200.
Composition [B] can be only be made of above-mentioned " be selected from polyether glycol (B1), polyether glycol (B2) and the polyether glycol (B3) at least a ", but also can contain the polyvalent alcohols beyond these that are no more than 50 quality %.
This examples of polyhydric alcohols be polyether glycol (will be equivalent to above-mentioned (B1), (B2) and polyvalent alcohol (B3) forecloses), polyester polyol, polycarbonate polyol, polyolefin polyhydric alcohol, animals and plants be polyvalent alcohol, as low molecular polylol below 300 of the molecular weight of chain extension agent, polymer polyatomic alcohol, halogen-containing polyvalent alcohol, phosphorated polyvalent alcohol, phenol type polyvalent alcohol (phenol base polyol) etc.In the middle of these, polyether glycol is preferred.
The overall proportion that polyether glycol (B1), polyether glycol (B2) and polyether glycol (B3) account for composition [B] is generally more than the 50 quality %, is preferably more than the 75 quality %, is preferably 100 quality % especially.When these overall proportion is lower than 50 quality %, the flame retardant resistance of formed rigid polyurethane slab foam and poor dimensional stability (with reference to comparative example 4 described later)
(composition [C])
The foam that uses among the present invention formation property composition is to contain the composition of water (composition [C]) as the water foaming formulation of whipping agent.With respect to the composition [B] of 100 mass parts, be preferably 2～10 mass parts as the content of the water of composition [C], more preferably 3～7 mass parts.When this content was excessive, not only the density of formed rigid polyurethane slab foam was lower than desired density (lighting), also can cause undercapacity, dimensional stability to reduce, and in addition, this rigid polyurethane slab foam becomes fragile.On the other hand, this content is when very few, and it is insufficient to foam, and density raises, and cost increases thus.
(composition arbitrarily)
In the scope of not damaging effect of the present invention, the foam that the present invention uses formation property composition can contain the composition except above-mentioned essential composition.
As this any composition, can enumerate fire retardant, suds-stabilizing agent, antioxidant, catalyzer, weighting agent, stablizer, tinting material etc.
The example that can be used as " fire retardant " of any composition use comprises organic halogen based compound, phosphorus series compound, (different) cyanogen urea acid derivative compound (nitrogenous compound of halogen), the nitrogenous compound (nitrogenous compound of halogen) except (different) cyanogen urea acid derivative compound, mineral compound etc.
Here, as " organic halogen based compound ", can enumerate tetrabromo-bisphenol (TBBA), dibromoneopentyl glycol, decabromodiphynly oxide (DBDPO), hexabromocyclododecane (HBCD), tribromophenol (TBP), ethylenebis tetrabromo phthalimide, brominated Polystyrene, TBBPA epoxy oligomer, the two dibromo propyl ether of TBBPA, ethylenebis pentabromo-hexichol etc.
In addition, as " phosphorus series compound ", can enumerate the ammonium polyphosphate based compounds such as condensation product of ammonium orthophosphate and urea, phosphoric acid esters such as trimethyl phosphite 99 (TMP), triethyl phosphate (TEP), tributyl phosphate, trioctyl phosphate, triphenylphosphate, tritolyl phosphate and octyl diphenyl phosphate, the condensed phosphoric acid esters classes such as poly phosphate that polymer quantizes, halogen-containing phosphoric acid ester such as tricresyl phosphate (chloropropyl) ester (TCPP), tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (dibromo neo-pentyl) ester etc.
In addition, as " (different) cyanogen urea acid derivative compound (nitrogenous compound of halogen) ", can enumerate trimeric cyanamide, sulfuric acid trimeric cyanamide, melamine phosphate, polyphosphoric acid melamine, melamine methylol, cyanogen urea acid trimethyl, cyanogen urea triethylenetetraminehexaacetic acid ester, cyanurodiamide, cyanuramide, 2,4, cyanogen urea acid derivatives such as 6-trihydroxy-anthocyanidin and melamine cyanurate; Isocyanuric acid derivatives such as cyamelide diimine, isomelamine, isocyanuric acid moinoimide, trimethylammonium carbodiimide, triethyl carbodiimide and isocyanuric acid etc.
In addition, as " nitrogenous compound (nitrogenous compound of halogen) except (different) cyanogen urea acid derivative ", can enumerate cyanamide derivatives such as Dyhard RU 100, guanylurea, guanidine, Guanidine Sulfamate 99 and biguanides; And urea derivativess such as urea, dimethylolurea, diacetyl urea, trimethyl-urea and N-benzoylureas etc.
In addition, as " mineral compound ", can enumerate magnesium hydroxide, aluminium hydroxide, sodium tetraborate, trimagnesium phosphate, sodium hypophosphate, zinc phosphate, antimonous oxide, antimony peroxide and nitrogenize guanidine, red phosphorus etc.
The example of " suds-stabilizing agent " that uses as any composition comprises " SZ-1171 ", " SZ-1649 ", " SZ-1666 ", " SZ-1694 ", " SZ-1671 ", " SZ-1711 ", " SZ-1127 ", " SZ-1919 ", " SZ-1718 ", " SZ-1692 ", " SF-2936F ", " SF-2937F ", " SF-2938F ", " SH-192 " (above) by Dow CorningCorporation manufacturing, " B-8444 ", " B-8460 ", " B-8465 ", " B-8870 ", " B-8871 ", " B-8232 ", " B-8466 ", " B-8467 " (above) by the manufacturing of go one Le De シ ユ ミ Star ト company, " F-373 ", " F-388 ", " F-394 ", " F-395 ", " X20-1748S ", " X20-1874 ", " X20-5042 ", " X20-5051 ", " X20-5043 " (above) etc. by SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing.
The example that can be used as " antioxidant " that any composition uses comprises that phenol is that antioxidant, phosphorous antioxidant, sulphur are antioxidant etc.
Here, as " phenol is antioxidant ", can enumerate that tetramethylolmethane four-[methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], 3,9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1, the 1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5] undecane, 1,3,5-three (2,6-dimethyl-3-hydroxyl-4-tertiary butyl benzyl) isocyanuric acid ester, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4, the 6-Three methyl Benzene, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids ethyl) calcium, 2,6-di-t-butyl-p-cresol, butylated hydroxy anisole (BHA), 2,6-di-t-butyl-4-ethylphenol, β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3,9-two [1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl]-2,4,8,10-four oxaspiros [5,5] undecane, 1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four-[methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane, two [3,3 '-two-(4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid] diol ester, 1,3,5-three (3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl)-guanamine, 4,6-(1H, 3H, 5H) triketone, tocopherols etc.
In addition, as " phosphorous antioxidant ", can enumerate alkyl phosphite, the phosphorous acid alkyl aryl ester, aryl phosphite, the phosphonous acid alkyl ester, phosphorus such as phosphonous acid aryl ester are stablizer, specifically, can enumerate two (tridecyl) pentaerythritol diphosphites, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, distearyl pentaerythrityl diphosphite, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-diphenylene phosphinate, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, 1,1,3-three (2-methyl-4-double tridecyl phosphorous acid ester-5-tert-butyl-phenyl) butane, the tricresyl phosphite phenylester, phosphorous acid phenylbenzene isodecyl ester, 4,4 '-butylidene-two (3-methyl-6-tert butyl phenyl double tridecyl) phosphorous acid ester, ring-type neopentane four bases two (octadecyl phosphorous acid ester), tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (single nonyl phenyl) ester, tricresyl phosphite (dinonyl phenyl) ester, the diiso decyl pentaerythritol diphosphites, 9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 10-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 10-oxygen in last of the ten Heavenly stems base-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, ring-type neopentane four bases two (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, ring-type neopentane four bases two (2,6-di-t-butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester etc.
In addition, as " sulphur is antioxidant ", can enumerate 3,3 '-thio-2 acid distearyl ester, tetramethylolmethane four (3-lauryl thiopropionate), 3,3 '-thiodipropionate dilauryl, 3,3 '-thio-2 acid myristyl ester, 3,3 '-thio-2 acid tricosyl ester, thiodipropionate dilauryl etc.
Can be used as " catalyzer " that any composition uses; can enumerate with triethylenediamine (TEDA); tetramethyl-hexamethylene-diamine (TMHMDA); five methyl diethylentriamine (PMDETA); dimethylcyclohexylam,ne (DMCHA); two dimethyl aminoethyl ethers (BDMAEA); the N-Methylimidazole; the trimethylammonium aminoethylpiperazine; tripropyl amine; triethylamine; amine compound such as N-methylmorpholine; dibutyltin diacetate; tin compounds such as dibutyl tin laurate; metal complexess such as Acetyl Acetone metal-salt; response type amine catalyst (dimethylethanolamine (DMEA) for example; N; N; N '-trimethylammonium amino ethyl ethanolamine; N, N-dimethylamino ethoxy ethanol) be the urethane catalyzer of representative.With respect to the composition [B] of 100 mass parts, the content of catalyzer is preferably below 2.5 mass parts, more preferably below 1.0 mass parts.
(manufacture method)
Manufacture method of the present invention is by allowing foam form the property composition react, and free foaming is made the method for rigid polyurethane slab foam under the open-top state.Foam formation property composition for example uses the composition of the two-part curable that is made of the 1st liquid and the 2nd liquid, and wherein said the 1st liquid is formed by composition [A], and described the 2nd liquid is mixed by composition [B], composition [C] and any composition and forms.In addition, can also use the composition of three part curables that are made of the 1st liquid, the 2nd liquid and the 3rd liquid, wherein said the 1st liquid is formed by composition [A], and described the 2nd liquid is formed by composition [B], and described the 3rd liquid is formed by composition [C] and any composition.
An example as concrete manufacture method, can enumerate: the 1st liquid (composition [A]) is mixed with the 2nd liquid (polyol blends that contains composition [B], composition [C] and any composition) with known stirring mixer (foaming machine), preparation foam formation property composition (mixture of foaminess), said composition is injected in the mould of open-top state and carries out free foaming, solidifying formation is the method (discontinuous method) of plate (piece).
Here, the floorage of the mould inside of the size of the plate that is formed by discontinuous method as decision is generally 0.25m 2(for example more than the 0.5m * 0.5m), be preferably 0.25m 2～6.0m 2(2.0m * 3.0m) for example.In addition, the height of the mould inside of decision plate size (thickness) is generally more than the 0.3m, is preferably 0.3～1.0m.
And manufacturing method according to the invention (discontinuous method) is even the large size [(0.25～6.0m that uses this mould to form 2) * (0.3～1.0m)] slab foam, coking can not take place in inside yet.
In addition, another example as manufacture method, can enumerate: the 1st liquid (composition [A]) is mixed with the 2nd liquid (polyol blends that contains composition [B], composition [C] and any composition) with known stirring mixer (foaming machine), preparation foam formation property composition (mixture of foaminess), said composition is ejected into continuously on the continuous circuit of open-top state and carries out free foaming, solidifying formation is the method (continuous processing) of plate.
Here, the width of the continuous circuit of the plate size that is formed by continuous processing as decision is generally more than the 0.5m, is preferably 0.5～3.0m.And, manufacturing method according to the invention (continuous processing), even the large-sized slab foam that is formed by this continuous circuit, coking can not take place in inside yet.
(rigid polyurethane slab foam of the present invention)
Rigid polyurethane slab foam of the present invention obtains by manufacture method of the present invention.Even the large-sized plate of the rigid polyurethane slab foam of the present invention ((0.25～6.0m that forms by discontinuous method for example 2The plate of) * (0.3～1.0m), the perhaps long slab of the width 0.5～3.0m that forms by continuous processing, thickness 0.3～1.0m), coking can not take place in inside yet.And this rigid polyurethane slab foam has low thermal conductivity, can through the time keep excellent flame and excellent in dimensional stability.Rigid polyurethane slab foam of the present invention has the separated foam structure, and specifically, the separated foam rate of measuring according to ASTMD2856 surpasses 75%.Because the separated foam rate surpasses 75%, rigid polyurethane slab foam has excellent thermal conductivity (excellent heat insulating ability).
(heat-insulating material for piping)
Heat-insulating material for piping of the present invention is processed rigid polyurethane slab foam of the present invention by severing and is obtained.Fig. 1 shows the stereographic map of heat-insulating material for piping of the present invention.Fig. 2 is the explanatory view shown in the part that thermal insulation material shown in Figure 1 is installed in the state on the pipeline is cut.Thermal insulation material 1A, 1B shown in Figure 1 has in the vertical the shape of cutting apart (dividing equally) cylinder and forming.Thermal insulation material 1A, 1B will be by processing shape by the hard slab foam severing that manufacture method of the present invention forms.In addition, " severing processing " also comprise " cutter is worn processing " etc.As shown in Figure 2, thermal insulation material 1A, 1B dispose in the mode that coats pipeline P surface, and be fixing by securing gear 3 under this state.The outside surface of thermal insulation material 1A, 1B can also coat with gas tightness sheet material or film.Thus, the gas (carbonic acid gas) that can prevent to constitute in the foamy bubble is replaced by air (than the thermal conductivity height of carbonic acid gas), and the result can keep the heat insulating ability at initial stage.As described " gas tightness sheet material or film ", can exemplify laminated film with one deck aluminium lamination.
Because thermal insulation material 1A, 1B are the materials of the tabular foam forming of hard that formed by aforementioned foam formation property composition, so it is bad etc. the bad order, the intensity that cause because of the intralamellar part coking can not to occur.In addition, thermal conductivity is low and have excellent heat insulating ability and heat retaining property, and has excellent flame and dimensional stability.
In addition, the shape of heat-insulating material for piping of the present invention and the installation method on pipeline be not limited to above-described those.
Embodiment
Embodiments of the invention below are described, yet the invention is not restricted to these embodiment.In addition, hereinafter, unless otherwise prescribed, " % " and " part " represents " quality % " and " mass parts " separately.In addition, the properties-correcting agent that uses in following preparation example is following compound.
(1) specific properties-correcting agent (d1): Diethylene Glycol and O-phthalic acid-respons and the polyester polyol (functional group's number=2, hydroxyl value=270mgKOH/g, number-average molecular weight=416) that obtains.(2) specific properties-correcting agent (d2): Diethylene Glycol and phthalic acid and hexanodioic acid reaction and the polyester polyol (functional group's number=2, hydroxyl value=230mgKOH/g, number-average molecular weight=488) that obtains.(3) specific properties-correcting agent (d3): Diethylene Glycol and O-phthalic acid-respons and the polyester polyol (functional group's number=2, hydroxyl value=255mgKOH/g, number-average molecular weight=440) that obtains.
(4) relatively use properties-correcting agent (d4): the 3-methyl isophthalic acid, 5-pentanediol and Beta-methyl-δ-Wu Neizhi reacts and the polyester polyol (functional group's number=2, hydroxyl value=112mgKOH/g, number-average molecular weight=1000) of acquisition.(5) relatively use properties-correcting agent (d5): the 3-methyl isophthalic acid, 5-pentanediol and Beta-methyl-δ-Wu Neizhi reacts and the polyester polyol (functional group's number=2, hydroxyl value=56mgKOH/g, number-average molecular weight=2000) of acquisition.(6) relatively use properties-correcting agent (d6): polyoxypropyleneglycol (functional group's number=2, hydroxyl value=281mgKOH/g, number-average molecular weight=400).(7) relatively use properties-correcting agent (d7): Diethylene Glycol and O-phthalic acid-respons and the polyester polyol (functional group's number=2, hydroxyl value=315mgKOH/g, number-average molecular weight=356) that obtains.(8) relatively use properties-correcting agent (d8): Diethylene Glycol and O-phthalic acid-respons and the polyester polyol (functional group's number=2, hydroxyl value=400mgKOH/g, number-average molecular weight=281) that obtains.(9) relatively use properties-correcting agent (d9): 1,4-butyleneglycol and hexanodioic acid react and the polyester polyol (functional group's number=2, hydroxyl value=112mgKOH/g, number-average molecular weight=1000) of acquisition.
(preparation example 1)
According to the prescription shown in the following table 1, the MDI (a1) that drops into 32.4 parts in the reaction vessel that is provided with stirrer, thermometer, water cooler and nitrogen ingress pipe (contains more than 70% 4, two nucleomes of 4 '-MDI), be heated to 60 ℃, add 12.4 parts specific properties-correcting agent (d1) then, this system 60 ℃ of stir abouts 2 hours, is carried out modification to MDI thus and handled.Then, in this reaction product (MDI of modification), add to mix 55.2 parts polymeric MDI (a2), obtain 100.0 parts the composition [A] (hereinafter referred to as " composition [A-1] ") that NCO content is 25.4% modified polyisocyanate that comprises thus.
Gained composition [A-1] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 1050mPas.The ratio of two nucleomes that contained in this composition [A-1] (unmodified MDI molecule) is 40%.In addition, the ratio for two nucleomes in the total amount (87.6 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 62%.
(preparation example 2)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 36.3 parts, the addition of specific properties-correcting agent (d1) is changed into 8.5 parts comes modification to handle MDI, in addition, operate equally with preparation example 1, obtain 100.0 parts the composition [A] (hereinafter referred to as " composition [A-2] ") that NCO content is 27.5% modified polyisocyanate that comprises.
Gained composition [A-2] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 284mPas.Two nucleomes in this composition [A-2] (unmodified MDI molecule) to contain proportional be 48%.In addition, the ratio for two nucleomes in the total amount (91.5 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 64%.
(preparation example 3)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 31.6 parts, the specific properties-correcting agent (d2) that adds 13.2 parts replaces specific properties-correcting agent (d1) to come modification to handle MDI, in addition, operate equally with preparation example 1, obtain 100.0 parts the composition [A] (hereinafter referred to as " composition [A-3] ") that NCO content is 25.4% modified polyisocyanate that comprises.
Gained composition [A-3] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 760mPas.Two nucleomes in this composition [A-3] (unmodified MDI molecule) to contain proportional be 40%.In addition, the ratio for two nucleomes in the total amount (86.8 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 62%.
(preparation example 4)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 32.0 parts, the specific properties-correcting agent (d3) that adds 12.8 parts replaces specific properties-correcting agent (d1) to come modification to handle MDI, in addition, operate equally with preparation example 1, obtain 100.0 parts the composition [A] (hereinafter referred to as " composition [A-4] ") that NCO content is 25.4% modified polyisocyanate that comprises.
Gained composition [A-4] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 910mPas.Two nucleomes in this composition [A-4] (unmodified MDI molecule) to contain proportional be 40%.In addition, the ratio for two nucleomes in the total amount (87.2 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 62%.
(preparation example 5)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 32.0 parts, the addition of specific properties-correcting agent (d1) is changed into 12.8 parts come modification to handle MDI and interpolation and mix 55.2 parts polymeric MDI (a2) and 3.0 parts triethyl phosphate (TEP) in gained reaction product (MDI of modification), in addition, operate equally with preparation example 1, obtain 103.0 parts the composition [A] (hereinafter referred to as " composition [A-5] ") that NCO content is 24.5% modified polyisocyanate that comprises.
Gained composition [A-5] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 1020mPas.Two nucleomes in this composition [A-5] (unmodified MDI molecule) to contain proportional be 38%.In addition, the ratio for two nucleomes in the total amount (87.2 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 62%.
(preparation example 6)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 31.0 parts, the addition of specific properties-correcting agent (d1) is changed into 13.8 parts come modification to handle MDI, in addition, operate equally with preparation example 1, obtain 100.0 parts the composition [A] (hereinafter referred to as " composition [A-6] ") that NCO content is 24.7% modified polyisocyanate that comprises.
Gained composition [A-6] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 1900mPas.Two nucleomes in this composition [A-6] (unmodified MDI molecule) to contain proportional be 36%.In addition, the ratio for two nucleomes in the total amount (86.2 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 62%.
(preparation example 7)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 28.9 parts, the properties-correcting agent (d4) of relatively using that adds 15.9 parts replaces specific properties-correcting agent (d1) to come modification to handle MDI, in addition, operate equally with preparation example 1, the NCO content that obtains 100.0 parts is 25.4% modified polyisocyanate (hereinafter referred to as " composition [a-7] ").
Gained composition [a-7] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 450mPas.Two nucleomes in this composition [a-7] (unmodified MDI molecule) to contain proportional be 43%.In addition, the ratio for two nucleomes in the total amount (84.1 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 61%.
(preparation example 8)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 27.1 parts, the properties-correcting agent (d5) of relatively using that adds 17.7 parts replaces specific properties-correcting agent (d1) to come modification to handle MDI, in addition, operate equally with preparation example 1, the NCO content that obtains 100.0 parts is 25.4% modified polyisocyanate (hereinafter referred to as " composition [a-8] ").
Gained composition [a-8] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 490mPas.Two nucleomes in this composition [a-8] (unmodified MDI molecule) to contain proportional be 45%.In addition, the ratio for two nucleomes in the total amount (82.3 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 60%.
(preparation example 9)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 34.3 parts, the properties-correcting agent (d6) of relatively using that adds 10.5 parts replaces specific properties-correcting agent (d1) to come modification to handle MDI, in addition, operate equally with preparation example 1, the NCO content that obtains 100.0 parts is 25.4% modified polyisocyanate (hereinafter referred to as " composition [a-9] ").
Gained composition [a-9] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 780mPas.Two nucleomes in this composition [a-9] (unmodified MDI molecule) to contain proportional be 38%.In addition, the ratio for two nucleomes in the total amount (89.5 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 63%.
(preparation example 10)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 39.0 parts, the addition of specific properties-correcting agent (d1) is changed into 5.8 parts come modification to handle MDI, in addition, operate equally with preparation example 1, the NCO content that obtains 100.0 parts is 29.0% modified polyisocyanate (hereinafter referred to as " composition [a-10] ").
Gained composition [a-10] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) is 138mPas.Two nucleomes in this composition [a-10] (unmodified MDI molecule) to contain proportional be 54%.In addition, the ratio that is used for two nucleomes of the total amount (94.2 parts) of blended polymeric MDI (a2) after MDI (a1) that modification handles and the modification is 65%.
(preparation example 11)
The polymeric MDI (a2) that preparation is used in preparation example 1～10 (polykaryon=19% that two nucleomes=40%, three nucleome=27%, four nucleome=9%, five nucleome or six nucleomes=5%, seven nucleome is above; NCO content=30.9%, viscosity (25 ℃)=170mPas).This is hereinafter referred to as " composition [a-11] ".
(preparation example 12)
According to the prescription shown in the following table 1, the input amount of MDI (a1) is changed into 30.2 parts, the addition of specific properties-correcting agent (d1) is changed into 14.6 parts come modification to handle MDI, in addition, operate equally with preparation example 1, the NCO content that obtains 100.0 parts is 23.8% modified polyisocyanate (hereinafter referred to as " composition [a-12] ").
Gained composition [a-12] does not have muddy, presents transparent liquid, and its viscosity (25 ℃) height is 3700mPas.Two nucleomes in this composition [a-12] (unmodified MDI molecule) to contain proportional be 35%.In addition, the ratio for two nucleomes in the total amount (85.4 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 61%.
(preparation example 13)
According to the prescription shown in the following table 1, with the input amount of MDI (a1) change into 33.0 parts, the properties-correcting agent (d7) of relatively using that adds 11.8 parts replaces specific properties-correcting agent (d1) to come modification to handle MDI, in addition, operate equally with preparation example 1, the NCO content that obtains 100.0 parts is 25.4% modified polyisocyanate.
The gained modified polyisocyanate presents the aqueous of muddiness, is not suitable as the constituent that foam forms the property composition.In addition, the viscosity of this modified polyisocyanate (25 ℃) is 450mPas.Two nucleomes in this modified polyisocyanate (unmodified MDI molecule) to contain proportional be 39%.In addition, the ratio for two nucleomes in the total amount (88.2 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 62%.
(preparation example 14)
According to the prescription shown in the following table 1, with the input amount of MDI (a1) change into 34.3 parts, the properties-correcting agent (d8) of relatively using that adds 10.5 parts replaces specific properties-correcting agent (d1) to come modification to handle MDI, in addition, operate equally with preparation example 1, the NCO content that obtains 100.0 parts is 25.4% modified polyisocyanate.
The gained modified polyisocyanate presents the aqueous of muddiness, is not suitable as the constituent that foam forms the property composition.In addition, the viscosity of this modified polyisocyanate (25 ℃) is 1050mPas.Two nucleomes in this modified polyisocyanate (unmodified MDI molecule) to contain proportional be 38%.In addition, the ratio for two nucleomes in the total amount (89.5 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 63%.
(preparation example 15)
According to the prescription shown in the following table 1, with the input amount of MDI (a1) change into 28.9 parts, the properties-correcting agent (d9) of relatively using that adds 15.9 parts replaces specific properties-correcting agent (d1) to come modification to handle MDI, in addition, operate equally with preparation example 1, the NCO content that obtains 100.0 parts is 25.4% modified polyisocyanate.
The gained modified polyisocyanate presents the aqueous of muddiness, is not suitable as the constituent that foam forms the property composition.In addition, the viscosity of this modified polyisocyanate (25 ℃) is 400mPas.Two nucleomes in this modified polyisocyanate (unmodified MDI molecule) to contain proportional be 43%.In addition, the ratio for two nucleomes in the total amount (84.1 parts) of blended polymeric MDI (a2) after MDI (a1) that handles in modification and the modification is 61%.
Figure A20078003487200271
*1) MDI (a1): contain 4 more than 70%, the MDI of 4 '-MDI (two nucleomes).
*2) polymeric MDI (a2): polymeric MDI (polykaryon=19% that two nucleomes=40%, three nucleome=27%, four nucleome=9%, five nucleome or six nucleomes=5%, seven nucleome is above of usefulness is added in the back; NCO content=30.9%).
(embodiment 1)
According to the prescription shown in the following table 2, use high pressure foaming machine to mix and spray 133.2 parts contain composition [B], composition [C] and the composition [A-1] (liquid temperature=20) (nco index=100) of the acquisition in preparation example 1 of the polyol blends of composition (liquid temperature=30 ℃) and 191.0 parts arbitrarily, prepare the foaminess composition.To be injected into interior dimensions from the composition of low pressure foaming machine ejection and be in the wooden die of open-top type of 600mm * 600mm * 600mm, measure the reaction times (cream time and foaming time) in foaming and the solidifying formation process.The result is in the lump shown in the table 2.From mixing the zero hour of operation, carry out stripping operation after 1 hour excessively, obtain rigid polyurethane slab foam.
(embodiment 2～6)
According to the prescription shown in the following table 2, to contain composition [B], composition [C] and the polyol blends of composition and composition [A] are that 100 mode is used according to nco index arbitrarily by the proportioning shown in the table 2 (amount), in addition, operation similarly to Example 1, carry out the implant operation that mixes operation (foaminess preparation of compositions), composition, the mensuration in reaction times (result is shown in the following table 2) and the stripping operation of polyol blends and composition [A], obtain various rigid polyurethane slab foams.
Table 2
Figure A20078003487200291
(table 2 is annotated (identical in following table 3))
*3) polyvalent alcohol (B1-1): addition EO and PO on tolylene diamine and the polyether glycol (B1) that forms, functional group's number=4, number-average molecular weight=561, hydroxyl value=400mgKOH/g, viscosity (25 ℃)=20000mPas, [EO]: [PO]=20: 80 (mass ratio).
*4) polyvalent alcohol (B2-1): addition PO on Sorbitol Powder and the polyether glycol (B2) that forms, functional group's number=6, number-average molecular weight=874, hydroxyl value=385mgKOH/g, viscosity (25 ℃)=8400mPas.
*5) polyvalent alcohol (B3-1): addition PO on sucrose and the polyether glycol that forms, functional group's number=8, number-average molecular weight=1069, hydroxyl value=420mgKOH/g, viscosity (25 ℃)=28000mPas.
*6) fire retardant (TCPP): tricresyl phosphate (chloropropyl) ester.
*7) suds-stabilizing agent (B-8460): " B-8460 " (manufacturing of go one Le De シ ユ ミ Star ト company).
*8) antioxidant (1): four-[methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester] methane " Irganox 1010 " (Ciba Specialty Chemicals Inc. manufacturing).
*9) antioxidant (2): two (tridecyl) pentaerythritol diphosphites " JPP-13R " (north of the city chemistry (strain) manufacturing).
(comparative example 1)
According to the prescription shown in the following table 3, use the composition [a-7] (nco index=100) of 191.0 parts preparation example 7 acquisitions to replace composition [A-1], in addition, operation similarly to Example 1, carry out the implant operation that mixes operation (foaminess preparation of compositions), composition, the mensuration in reaction times (result is shown in the following table 3) and the stripping operation of polyol blends and composition [a-7], obtain rigid polyurethane slab foam.This example is to use the comparative example that is lower than the modified polyisocyanate that the polyester polyol modification of 150mgKOH/g handle to obtain by hydroxyl value.
(comparative example 2)
According to the prescription shown in the following table 3, use the composition [a-8] (nco index=100) of 167.0 parts preparation example 8 acquisitions to replace composition [A-1], in addition, operation similarly to Example 1, carry out the implant operation that mixes operation (foaminess preparation of compositions), composition, the mensuration in reaction times (result is shown in the following table 3) and the stripping operation of polyol blends and composition [a-8], obtain rigid polyurethane slab foam.This example is to use the comparative example that is lower than the modified polyisocyanate that the polyester polyol modification of 150mgKOH/g handle to obtain by hydroxyl value.
(comparative example 3)
According to the prescription shown in the following table 3, use the composition [a-9] (nco index=100) of 191.0 parts preparation example 9 acquisitions to replace composition [A-1], in addition, operation similarly to Example 1, carry out the implant operation that mixes operation (foaminess preparation of compositions), composition, the mensuration in reaction times (result is shown in the following table 3) and the stripping operation of polyol blends and composition [a-9], obtain rigid polyurethane slab foam.This example is to use the comparative example of being handled the modified polyisocyanate that obtains by modified by polyether glycol.
(comparative example 4)
According to the prescription shown in the following table 3, use 133.4 parts contain polyhydroxy reactant, composition [C] and the polyol blends of composition and 199.0 parts composition [A-1] (nco index=100) arbitrarily, in addition, operation similarly to Example 1, carry out the implant operation that mixes operation (foaminess preparation of compositions), composition, the mensuration in reaction times (result is shown in the following table 3) and the stripping operation of polyol blends and composition [A-1], obtain rigid polyurethane slab foam.This example is that the overall proportion that polyether glycol (B1), polyether glycol (B2) and polyether glycol (B3) account for whole polyhydroxy reactant is lower than 50% comparative example.
(comparative example 5)
According to the prescription shown in the following table 3, use the composition [a-10] (nco index=100) of 191.0 parts preparation example 10 acquisitions to replace composition [A-1], in addition, operation similarly to Example 1, carry out the implant operation that mixes operation (foaminess preparation of compositions), composition, the mensuration in reaction times (result is shown in the following table 3) and the stripping operation of polyol blends and composition [a-10], obtain rigid polyurethane slab foam.This example is to use NCO content to surpass the comparative example of 28.0% modified polyisocyanate.
(comparative example 6)
According to the prescription shown in the following table 3, use the composition [a-11] (nco index=100) of 157.0 parts preparation example 11 acquisitions to replace composition [A-1], in addition, operation similarly to Example 1, carry out the implant operation that mixes operation (foaminess preparation of compositions), composition, the mensuration in reaction times (result is shown in the following table 3) and the stripping operation of polyol blends and composition [a-11], obtain rigid polyurethane slab foam.This example is to use the comparative example of unmodified polymeric MDI (NCO content=30.9%).
(comparative example 7)
According to the prescription shown in the following table 3, use the composition [a-12] (nco index=100) of 204.0 parts preparation example 12 acquisitions to replace composition [A-1], in addition, operation similarly to Example 1, that attempts polyol blends and composition [a-12] mixes operation (foaminess preparation of compositions), but composition [a-12] can not be in the pipeline of foaming machine, in the flexible pipe with the flow circulation of regulation, so hang up.This example is to use NCO content to be lower than the comparative example of 24.0% modified polyisocyanate (3700mPas).
Table 3
*11) polyvalent alcohol (b-1): the polyether glycol that addition PO is obtained on glycerine, functional group's number=3, number-average molecular weight=600, hydroxyl value=281mgKOH/g, viscosity (25 ℃)=270mPas.
*12) polyvalent alcohol (b-2): addition EO and PO on glycerine and the polyether glycol that obtains, functional group's number=3, number-average molecular weight=6000, hydroxyl value=28mgKOH/g, viscosity (25 ℃)=1100mPas.
*13) polyvalent alcohol (b-3): addition PO on glycerine and the polyether glycol that obtains, functional group's number=3, number-average molecular weight=250, hydroxyl value=673mgKOH/g, viscosity (25 ℃)=950mPas.
*10) catalyzer (Toyocat L33). " TOYOCAT L33 " (East ソ one (strain) manufacturing).
(evaluation of slab foam)
(600mm * 600mm * 600mm), at room temperature left standstill after the demoulding 24 hours measures and estimates following project (1)～(7) then for each rigid polyurethane slab foam that embodiment 1～6 and comparative example 1～6 obtains.In addition, in the slab foam of the comparative example that is evaluated as " * " 5 of following (2) and comparative example 6, can not implement the mensuration and the evaluation of following (3)～(7).The result is shown in the following table 4.
(1) density:, measure the test film from slab foam, cut (size and the quality of 200mm * 200mm * 200mm), bulk density (kg/m according to JIS K7222 3).
(2) have or not inner coking: cut off slab foam, observe inside, according to the pyrogenic situation occurred of following benchmark evaluation.
" zero ": do not find to take place coking fully.
" △ ": find to take place slight coking (foam center portion becomes light brown a little).
" * ": obviously find to take place coking (foam center portion overstrike).
(3) separated foam rate: use the test film (30mm * 30mm * 130mm (foaming direction)) that cuts from slab foam, measure separated foam rate (%) according to ASTM D2856.
(4) thermal conductivity: cut off slab foam (section) abreast with the foaming direction, the test film of preparation 200mm (foaming direction) * 200mm * 25mm is according to JISA1412 and use thermal conductivity determinator (Auto A) mensuration.
(5) combustion test (initial value): according to JIS A9511, measure burning extent and combustion time, estimate the flame retardant resistance of slab foam according to these values.
(6) combustion test (through the time after): (13mm * 50mm * 150mm) placed 30 days under 23 ℃ of temperature, 50% relative humidity environment the test film that will cut from slab foam, similarly operate then with above-mentioned (5), measure burning extent and combustion time, according to these values estimate through the time after the flame retardant resistance of slab foam.
(7) dimensional stability (mensuration of volume change): (volume change of 50mm * 50mm * when 50mm) leaving standstill certain hour under following atmosphere is estimated dimensional stability to measure the test film that cuts from slab foam.
80 ℃ * 2 days.
-20 ℃ * 2 days.
Figure A20078003487200361
Utilizability on the industry
Rigid polyurethane slab foam of the present invention can be used as for the manufacture of requiring thermal insulation The employed goods of various uses (the especially various pipeline thermal insulating materials of property and heat insulating ability Material) raw material uses.

Claims (11)

1. the manufacture method of a rigid polyurethane slab foam, it is characterized in that, allow foam form the property composition react, free foaming under the open-top state, wherein, described foam forms the property composition and contains: the NCO content that at least a portion obtained of [A] poly methylene poly phenyl poly isocyanate by containing 30～80 quality % diphenylmethanediisocyanates with modifier modification is 24.0～28.0% modified polyisocyanate, and described properties-correcting agent is that the polyester polyol of 150～300mgKOH/g constitutes by hydroxyl value; [B] contain total amount be 50 quality % above to be selected from the tolylene diamine be the polyether glycol (B1) of initiator, be the polyether glycol (B2) of initiator with the Sorbitol Powder and be at least a polyhydroxy reactant in the polyether glycol (B3) of initiator with sucrose; And [C] whipping agent of constituting by water.
2. the manufacture method of rigid polyurethane slab foam according to claim 1 is characterized in that, the hydroxyl value that is used to obtain the employed properties-correcting agent of aforementioned composition [A] is 200～300mgKOH/g, and the NCO content of this composition [A] is 24.5～27.5%.
3. the manufacture method of rigid polyurethane slab foam according to claim 1 and 2, it is characterized in that, being used to obtain the employed properties-correcting agent of aforementioned composition [A] is by being selected from ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, triethylene glycol and 3-methyl isophthalic acid, at least a polyvalent alcohol in the 5-pentanediol and the polyester polyol that is selected from least a polyprotonic acid acquisition in phthalic acid, m-phthalic acid, terephthalic acid and the hexanodioic acid.
4. the manufacture method of rigid polyurethane slab foam according to claim 1 and 2 is characterized in that, is used to obtain the employed properties-correcting agent of aforementioned composition [A] and is the polyester polyol that is obtained by Diethylene Glycol and phthalic acid and/or hexanodioic acid.
5. according to the manufacture method of each described rigid polyurethane slab foam of claim 1～4, it is characterized in that aforementioned composition [A] is to mix with the remainder of poly methylene poly phenyl poly isocyanate afterwards by a part of handling poly methylene poly phenyl poly isocyanate with the aforementioned modifiers modification to obtain.
6. the manufacture method of rigid polyurethane slab foam according to claim 5 is characterized in that, confession is diphenylmethanediisocyanate (two nucleomes) in the part of the aforementioned poly methylene poly phenyl poly isocyanate that modification is handled.
7. according to the manufacture method of each described rigid polyurethane slab foam of claim 1～6, it is characterized in that aforementioned composition [B] comprises polyether glycol (B1), polyether glycol (B2) and polyether glycol (B3).
8. a rigid polyurethane slab foam is characterized in that, its each described manufacture method by claim 1～7 obtains.
9. polyurethane slab foam according to claim 8, it is by having 0.25m with aforementioned foam formation property composition 2Free foaming forms in the mould of the open-top state of above floorage.
10. polyurethane slab foam according to claim 8, it forms property composition free foaming and forms by being ejected into aforementioned foam on the continuous circuit of open-top state continuously with the width more than the 0.5m.
11. a heat-insulating material for piping, its each described rigid polyurethane slab foam by severing processing claim 8～10 obtains.
CN2007800348728A 2006-09-19 2007-09-13 Process for producing rigid polyurethane slab foam, rigid polyurethane slab foam, and heat-insulating material for piping Expired - Fee Related CN101516946B (en)

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* Cited by examiner, † Cited by third party
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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3001462A1 (en) * 1980-01-17 1981-09-10 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING URETHANE AND / OR ISOCYANURATE GROUPS OF FOAMS
JP3254664B2 (en) * 1992-03-03 2002-02-12 日本ポリウレタン工業株式会社 Method for producing flexible polyurethane foam slab
NZ335208A (en) * 1996-11-04 2000-11-24 Huntsman Ici Chem Llc Rigid polyurethane foams
SG55257A1 (en) * 1996-12-30 1998-12-21 Koninkl Philips Electronics Nv Receiver with a turnable parallel resontant circuit
JP3777588B2 (en) * 1999-06-22 2006-05-24 日本ポリウレタン工業株式会社 Flexible polyurethane slab foam and method for producing the same
JP2002128850A (en) * 2000-10-23 2002-05-09 Nippon Polyurethane Ind Co Ltd Polyisocyanate composition for hard polyurethane foam and method of manufacturing hard polyurethane foam using the same
KR100507847B1 (en) * 2003-03-19 2005-08-17 한국가스공사 Hard polyurethane foam composition and insulation for keeping coolness using it

Cited By (4)

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