CN1306549A - Process for producing polyurethane foamed plastic - Google Patents
Process for producing polyurethane foamed plastic Download PDFInfo
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- CN1306549A CN1306549A CN 99807536 CN99807536A CN1306549A CN 1306549 A CN1306549 A CN 1306549A CN 99807536 CN99807536 CN 99807536 CN 99807536 A CN99807536 A CN 99807536A CN 1306549 A CN1306549 A CN 1306549A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G2410/00—Soles
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A process for producing a polyurethane foam which comprises reacting: an isocyanate composition ingredient A containing an isocyanate-terminated prepolymer obtained by condensation-polymerizing a polyester polyol resulting by reacting a polybasic acid ingredient comprising an aromatic polybasic acid and an aliphatic polybasic acid in a molar ratio of 0.05 to 0.4 with a polyhydric alcohol ingredient and a polyether polyol having two to six functional hydroxyl groups on the average and a number-average molecular weight of 1,500 to 20,000 with an organic polyisocyanate; with a polyol ingredient ingredient B comprising a polyester polyol or polyether polyol, a chain extender, a foaming agent, and a catalyst for urethane formation. By the process, a polyurethane foam which has excellent mechanical strength, is significantly reduced in the development of pinholes or shrinkage marks on the surface, and is suitable for use especially as a shoe sole can be produced in a short demolding time.
Description
Technical field
The present invention relates to the manufacture method of urethane foam.More particularly, relate to the manufacture method that has high mechanical strength, is suitable as the urethane foam of sole etc.
Background technology
In the past, good as dimensional stability, as to shrink little low density polyurethane foam manufacture method, the method that has proposed have the method (Japan's special permission openly communique nineteen ninety No. 105814) of use obtains polyester polyol, specific polyether polyol with the organic multiple isocyanate reaction isocyanate prepolymer.
Yet, this method is owing to use the part of polyether polyol composition as prepolymer, therefore, compare with the method for only using the isocyanate prepolymer that obtains by polyester polyol, time (from the mould time) length, productivity that urethane foam is taken out from molding metal mold are low, and the physical strength of gained urethane foam descends.
As the manufacture method of the urethane foam of physical strength excellence, the method that has proposed has the mol ratio of using terephthalic acid composition/aliphatic polybasic acid acid to be the polyester polyol of the 0.05-0.3 method (the open communique of Japan's special permission 1997 No. 302065) as raw material.
According to this method, can obtain the urethane foam of physical strength excellence, but in recent years, people expect to develop that a kind of contraction is littler, the better urethane foam of dimensional stability.
The objective of the invention is, provide a kind of can be short make from the mould time and have excellent physical strength and surperficial rare pin hole and contraction, especially be suitable as the method for sole with the urethane foam of urethane foam.
Above-mentioned and other purposes of the present invention can be known from the following description.
Disclosure of an invention
The invention provides a kind of manufacture method of the urethane foam with the reaction of following A composition and B composition:
The A composition: isocyanate composition, it contains mol ratio by aromatic series polyprotonic acid/aliphatics polyprotonic acid is the polyprotonic acid composition of 0.05-0.4 and polyester polyol that the polyhydroxy reactant polycondensation obtains and is that 2-6 and number-average molecular weight are that to react the end that obtains with organic multiple isocyanate be the prepolymer of isocyanic ester for the polyether polyol of 1500-20000 by average hydroxyl functional group number
The B composition: polyhydroxy reactant, it contains polyester polyol or polyether polyol, chain extension agent, whipping agent, urethane catalysts
Preferred forms of the present invention
" terminal prepolymer as isocyanic ester " (hereinafter to be referred as " prepolymer ") that use in the A composition is meant the resultant of reaction of polyisocyanates and polyvalent alcohol, and it does not contain the free hydroxyl.This prepolymer is not make the residual relative quantity of free hydroxyl (representing with the isocyanate group that exists in the reaction mixture and the ratio of the number of hydroxyl, as follows) make polyisocyanates and polyol reaction and obtain in prepolymer.For the free hydroxyl is not residued in the prepolymer, this relative quantity is preferably in more than 2.If this relative quantity is greater than 2, then free polyisocyanates (that is, not with the polyisocyanates of polyol reaction) may be residual.This free polyisocyanates can influence the NCO% of the isocyanate composition of A composition.Consider that from storage stability with in the angle of the liquid state of room temperature this relative quantity is preferably below 50, more preferably below 30.
" average hydroxyl functional group number " is meant the average functional group number (hydroxyl value of each molecule) of the polyhydric alcohol composition the when number of the active hydrogen of average each molecule of supposing the starting raw material that uses in the manufacturing is counted as the average functional group of starting raw material, but because terminal unsaturation, actual numerical value will be hanged down.In addition, " hydroxy functional group number " is meant the hydroxyl value of each molecule.
" isocyanate composition " that uses in the A composition also can contain the free polyisocyanates outside prepolymer.
Polyester polyol in the A composition obtains by the polycondensation of polyprotonic acid composition and polyhydroxy reactant, and in described polyprotonic acid composition, the mol ratio of aromatic series polyprotonic acid/aliphatics polyprotonic acid is 0.05-0.4.
The example of aromatic series polyprotonic acid has:
Aromatic dicarboxylic acid classes such as terephthalic acid, m-phthalic acid, phthalate anhydride, phthalic acid;
The phthalic acid derivative that following formula is represented:
In the formula, R1 represents the aralkyl, halogen atom, the alkoxyl group of a 1-4 carbon atom, the aryloxy that hydroxyl maybe can have a substituent 6-12 carbon atom of aryl, a 7-13 carbon atom of alkyl, a 6-12 carbon atom of 1-4 carbon atom;
The naphthalene derivatives that following formula is represented:
In the formula, R2 represents the aralkyl, halogen atom, the alkoxyl group of a 1-4 carbon atom, the aryloxy that hydroxyl maybe can have a substituent 6-12 carbon atom of aryl, a 7-13 carbon atom of alkyl, a 6-12 carbon atom of hydrogen atom, a 1-4 carbon atom;
These aromatic series polyprotonic acids can use separately or share more than two kinds.In these aromatic series polyprotonic acids, aromatic dicarboxylic acid, 4-dimethylamino methyl phenyl acid anhydrides, 1,4-naphthalene dicarboxylic acids and 2, the 6-naphthalene dicarboxylic acids is suitable especially, wherein, is good with terephthalic acid, phthalate anhydride and phthalic acid especially.
The example of aliphatics polyprotonic acid has oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, the ninth of the ten Heavenly Stems dicarboxylic acid, the last of the ten Heavenly stems dicarboxylic acid, undecane dicarboxylic acid, dodecanedicarboxylic acid, tridecane dicarboxylic acid, tetradecane dicarboxylic acid, pentadecane dicarboxylic acid, the hexadecane dicarboxylic acid, heptadecane dicarboxylic acid, the octadecane dicarboxylic acid, the nonadecane dicarboxylic acid, the eicosane dicarboxylic acid, the heneicosane dicarboxylic acid, the docosane dicarboxylic acid, the tetracosane dicarboxylic acid, the octacosane dicarboxylic acid, saturated aliphatic dicarboxylic acids such as laccerane dicarboxylic acid; Unsaturated aliphatic dicarboxylic acid such as toxilic acid, fumaric acid, methylene-succinic acid; Dimeracid, citric acid, tartrate, spiculisporic acid etc., these aliphatics polyprotonic acids can use separately or share more than two kinds separately.In these aliphatics polyprotonic acids, saturated aliphatic dicarboxylic acids (especially hexanodioic acid) is because fine resistance to hydrolysis and the tensile strength of gained urethane foam with excellence of giving of energy safe, cheap, therefore suitable especially with taking into account.
Be used for polyprotonic acid composition of the present invention and contain aromatic series polyprotonic acid and aliphatics polyprotonic acid, but in the scope that does not influence the object of the invention, also can contain other polyprotonic acid compositions.Described other polyprotonic acid compositions for example have tetrabromo-benzene dioctyl phthalate etc. to contain dicarboxylic acid of halogen etc.
For zero pour being increased and it being in a liquid state at (about forming temperature: 40-50 ℃) under the molding condition, in above-mentioned polyprotonic acid composition, the mol ratio of aromatic series polyprotonic acid/aliphatics polyprotonic acid should be more than 0.05, preferably more than 0.08, consider when being shaped and penetrate easily and injection, this mol ratio should be below 0.4, preferably below 0.2.
The example of polyhydroxy reactant has ethylene glycol, propylene glycol, 1, ammediol, 1,4-propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, glycol ether etc., these polyhydroxy reactants can use separately or share more than two kinds separately.In these polyhydroxy reactants, from the angle of the urethane foam that can obtain having rerum naturas such as excellent tensile strength, preferred ethylene glycol and 1,4-butyleneglycol.Ethylene glycol and 1, the 4-butyleneglycol can use separately separately, also can share.
Polyester polyol is by obtaining polyprotonic acid composition and polyhydroxy reactant polycondensation.
The reaction of polyprotonic acid composition and polyhydroxy reactant is polycondensation, two ends of gained polyester polyol must be hydroxyls, therefore, on stoichiometry, that the equivalence ratio (COOH/OH) of the COOH group of polyprotonic acid composition and the OH group of polyhydroxy reactant cans be compared to most is 1 little-and a little.
The method that the polycondensation method of polyprotonic acid composition and polyhydroxy reactant so long as be generally used for is made polyester then is not particularly limited.
Consider from the angle of operability, the used polyester polyol that obtains by the polycondensation of polyprotonic acid composition and polyhydroxy reactant be preferably in 40 ℃ be in a liquid state, viscosity (60 ℃) is below 10000mPas.
The average hydroxyl functional group number of the polyether polyol that uses in the A composition is 2-6, and number-average molecular weight is 1500-20000.From avoiding causing the angle of rerum natura decline to be considered owing to the increase of molecule, average hydroxyl functional group number should be more than 2, consider that from the angle of the flexibility that improves urethane foam average hydroxyl functional group number should be below 6, preferably below 4, better below 3.In addition, the angle consideration of shrinking from urethane foam is difficult for, number-average molecular weight should consider that from shortening from the angle of mould time number-average molecular weight should be below 20000 more than 1500.
The example of polyether polyol adduction on the terminal hydroxyl of polyoxypropylene glycol is arranged oxyethane, with respect to the number-average molecular weight of 1 hydroxyl be polyvalent alcohol (to call PPG in the following text) at the polyoxypropylene more than 1500, the number-average molecular weight that obtained by the ring-opening polymerization of tetrahydrofuran (THF) is at the polyoxybutylene glycol more than 1500 (to call PTMG in the following text), their mixture etc.
PPG in the gained urethane foam, can be used as soft chain segment because the repeating unit of its oxypropylene chain is long effectively, plays the effect that improves elongation performance and bending property, and is therefore, suitable especially.Angle from the effect of the soft chain segment of effective performance oxypropylene chain, in PPG, molecular weight with respect to 1 hydroxyl should be more than 1500, preferably more than 2000, better more than 3000, from the angle of the viscosity handled, should be below 20000, preferably below 15000, better below 8000.
PPG is a starting raw material with the compound bearing active hydrogen that has more than 2, by it being carried out common oxirane opening, the addition of ethylene oxide block ground being made in the method for molecular end etc. again.
The example of the starting raw material of PPG has polyvalent alcohol, polyphenol, polyamines, alkanolamine etc.Its object lesson has ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Glycerol dimer, dextrose, sucrose, dihydroxyphenyl propane, quadrol and their modified product etc.These raw materials can use separately separately, or share more than two kinds.
The oxirane that adds in opening on the above-mentioned raw materials comprises oxyethane, propylene oxide, 1,2-butylene oxide ring, 2,3-butylene oxide ring, Styrene oxide 98min., their multipolymer etc.In these oxiranes, preferably use propylene oxide separately, perhaps be main component (more than the 50 weight %) with the propylene oxide, itself and other oxirane is share, make their random copolymerization or block copolymerization.
After starting raw material and oxirane reaction, the reactivity of the urethane when making urethane foam in order to improve is preferably carried out the block addition reaction of oxyethane, makes terminal hydroxyl become primary hydroxyl.The reactivity of the urethane when improve making urethane foam, shorten from the mould time, improve the angle consideration that the balance between resinifying speed and the foamed speed is shunk to avoid urethane foam, the primary hydroxyl rate (primary hydroxyl number/total hydroxy) of the terminal hydroxyl that is undertaken by oxyethane is preferably more than 50%, better more than 70%.
Yet, if the inner and terminal oxyethylene group content of PPG increases, then wetting ability increases, moisture is attracted, resistance to hydrolysis descends, and therefore, the oxyethylene group content among the PPG is preferably in below the 35 weight %, consider that from the angle of the primary hydroxyl rate of terminal hydroxyl the oxyethylene group content among the PPG is preferably in more than the 5 weight %.If the primary hydroxyl rate of the molecular weight with respect to 1 hydroxyl, oxyethylene group content and the terminal hydroxyl of polyether polyol integral body is in above-mentioned scope, then PPG can prepare by several polyoxyalkylene polyols are mixed.
Above-mentioned PTMG has the character that improves mechanical propertys such as intensity from its molecular structure.Consider from angle as the availability of the soft chain segment of inferior oxygen-butyl chain, the number-average molecular weight of PTMG should be more than 1500, preferably more than 1800, consider from keeping liquid angle in the processing service temperature, the number-average molecular weight of PTMG should be below 20000, preferably below 3000, better below 2300.
The example of the organic multiple isocyanate that uses in the A composition has tolylene diisocyanate, m-phenylene diisocyanate, right-phenylene diisocyanate, Xylene Diisocyanate, 4,4 ＇-diphenylmethanediisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, polymethylene polyphenylene vulcabond, 3,3 '-dimethyl-biphenyl-4,4 '-vulcabond, 3,3 ＇-dimethyl-4,4 ＇-diphenylmethanediisocyanate, 3,3 '-two chloro-biphenyl-4,4 '-vulcabond, naphthalene-1, organic polyisocyanate compounds such as 5-vulcabond, their modified product (as the carbodiimide modified product) etc., these organic multiple isocyanate monomers can use separately, also can share more than two kinds.Wherein, especially with 4,4 '-the independent use of diphenylmethanediisocyanate or this 4,4 '-the share of diphenylmethanediisocyanate and its carbodiimide modified product to good.
The isocyanate composition of A composition can be by with the mixture reaction of organic multiple isocyanate and polyester polyol and polyether polyol or by organic multiple isocyanate is prepared successively or with arbitrary order and polyester polyol and polyether polyol reaction.In addition, also the polyester type isocyanate composition that contains the polyester type prepolymer can be mixed the back uses with the polyether-type isocyanate composition that contains the polyether-type prepolymer, described polyester type prepolymer is reacted by polyester polyol and organic multiple isocyanate and obtains, and described polyether-type prepolymer is reacted by polyether polyol and organic multiple isocyanate and obtains.Above-mentioned polyester type isocyanate composition and polyether-type isocyanate composition can contain the free organic multiple isocyanate separately.Polyester polyol/polyether polyol (weight ratio) is good with 1/9-9/1, is good with 1/5-5/1 especially.When above-mentioned polyester type isocyanate composition and polyether-type isocyanate composition were share, polyester polyol/polyether polyol (weight ratio) of being obtained by calculating was good with 1/9-9/1, is good with 1/5-5/1 especially.
When preparing the isocyanate composition of A composition, optionally, can add additive.
When the example of above-mentioned additive is included in preparation above-mentioned polyester polyol or polyether polyol optionally and the additive that adds; and, can use phosphate cpds such as chloride of acid such as sour gas such as hydrogen chloride gas, sulfur dioxide gas, Acetyl Chloride 98Min., Benzoyl chloride, isophthalyl chloride, phosphoric acid, phosphoric acid-ethyl ester, diethyl phosphoric acid etc. to prevent isocyanic ester oneself polymeric reagent for preventing above-mentioned isocyanate prepolymer oneself polymerization.These additives can use separately, also can share more than two kinds.
Cause being difficult to being shaped for avoiding viscosity to increase with the low pressure foaming machine, the NCO% of isocyanate composition should be more than 15%, preferably 17 ℃ (more than, cause the Measuring Precision of foaming machine to descend for avoiding viscosity degradation, above-mentioned NCO% should be below 25%, preferably below 22%.
The average hydroxyl functional group number of the polyester polyol of B composition or polyether polyol is preferably 2-6, and number-average molecular weight is preferably 500-6000.The example of polyester polyol has ethylene glycol, glycol ether, propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, methyl pentanediol, 1,6-hexylene glycol, TriMethylolPropane(TMP), glycerine, tetramethylolmethane, Glycerol dimer, dextrose, Sorbitol Powder etc. at least-at least a diprotic acid polycondensation such as kind of polyvalent alcohol and oxalic acid, propanedioic acid, Succinic Acid, hexanodioic acid, sebacic acid, dimeracid and the polyester polyol that obtains or polycaprolactone type polyvalent alcohol etc., this polyester polyol can contain the polyester polyol that uses, polycarbonate polyol etc. in the A composition.The example of polyether polyol has polyether polyols such as polypropylene glycol, polyoxybutylene glycol etc., and this polyether polyol can contain the polyether polyol that uses in the A composition.Polyester polyol and polyether polyol can use separately separately, also can share more than two kinds.Wherein, consider, being good by 4-butyleneglycol and hexanodioic acid or the polyester polyol that obtains by ethylene glycol and glycol ether and hexanodioic acid polycondensation from the angle that improves rerum natura.
The chain extension agent that uses in the B composition preferably hydroxy functional group number is 2-6, the molecular weight polyvalent alcohol as 62-499.If the hydroxy functional group number is more than 2, then can obtain fully if below 6, then can improving flexibility from mould and rerum natura.In addition, if molecular weight in this scope, then can shorten from the mould time.Consider that from angle the amount of chain extension agent should be equivalent to the 2-30 weight % of polyester polyol or polyether polyol, is good with 5-25 weight % especially from mould and rerum natura.
The representative example of chain extension agent has ethylene glycol, glycol ether, propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, methyl pentanediol, 1, polyvalent alcohols such as 6-hexylene glycol, TriMethylolPropane(TMP), glycerine, tetramethylolmethane, Glycerol dimer, dextrose, Sorbitol Powder; Quadrol and 1, aliphatic polyamines such as 6-hexanediamine; Aromatic polyamine; Alkanolamines such as diethanolamine, trolamine, diisopropanolamine (DIPA) etc.These chain extension agents can share separately or more than two kinds.
The example of whipping agent has fluorinated hydrocarbons such as water, trichlorofluoromethane, Refrigerant 12, difluorotrichloroethane etc., and these whipping agents can use separately or share more than two kinds.
The example of urethane catalyst for reaction has triethylamine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N '-tetramethyl-hexamethylene-diamine, 1,2-methylimidazole, N, tin compounds such as tertiary amines such as N '-diethyl benzylamine, tin acetate (III), stannous octoate (II), tin laurate (II), dibutyl tin laurate, two oxysuccinic acid dibutyl tins, oxalic acid dioctyl tin, dichloride dibutyl tin etc.These urethane catalyzer can use separately, also can share more than two kinds.
Optionally, the B composition can contain an amount of surfactant, stablizer, pigment etc.
The example of surfactant has aniorfic surfactant such as siloxane type surfactants, soap, sulfuric acid, phosphate ester salt, sulfonate such as the dimethyl polysiloxane of dimethyl polysiloxane, polyoxyalkylene polyol modification, the dimethyl polysiloxane of alkylen glycol-modified etc.
The example of stablizer has butylated hydroxytoluene, tetramethylolmethane four, and (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester), iso-octyl-3-) 3,5-di-tert-butyl-hydroxy phenyl (antioxidants such as phosphorons acid compound such as Hinered phenols free radical scavenger, phosphorous acid, triphenylphosphate, triethyl phosphate, triphen phosphorus such as propionic ester; The UV light absorber such as condenses of 2-(5-methyl-2-hydroxy phenyl) benzotriazole, methyl-3-(the 3-tertiary butyl-5-(2H-benzotriazole-2-yl)-4-hydroxy phenyl) propionic ester and polyoxyethylene glycol etc.
It is the mineral dye of representative that the example of pigment has with the transition metal salt, be pigment dyestuff, carbon dust of representative etc. with the azo-compound, but the invention is not restricted to these examples.
A composition and B composition are liquid state at 40 ℃, and therefore, the forming temperature about 40-50 ℃ for example can be used to make urethane foam and well without any problem.
In the present invention, with the A composition with the B composition so that the isocyanurate equivalent in the A composition with the B composition in the hydroxyl of isocyanate reaction and the equivalent of water on calculating consistent mixture ratio with forming mill mixing, stirring, injection molding mould in, foaming, make the urethane foam shaping thus.More particularly, for example, usually with basin etc. with A composition and B composition separately about temperature adjustment to 40 ℃, with mixing injection type foaming machine automatically, mixing foaming machine such as ejaculation type foaming machine automatically and make A composition and the reaction of B composition, can make the urethane foam shaping thus then.
With after the B composition mixes, usually, make urethane foam molding such as form at the bottom of the polyurethane shoe A composition with temperature adjustment to about 40-60 ℃ forming metal mould.
Like this, the density of the molding of the urethane foam that obtains with manufacture method of the present invention considers from the angle that can obtain sufficient mechanical and low densityization, in the practicality with 0.15-1.0g/cm
3Being advisable, is 0.2-0.6g/cm preferably
3
Production Example 1 (manufacturing of polyester polyol A～G)
In four neck flasks, put into after aliphatics polyprotonic acid, aromatic series polyprotonic acid and the polyvalent alcohol of kind shown in the table 1 and quantity, stirring rod, dehydrating tube, nitrogen ingress pipe and thermometer are contained on this flask.
Then, nitrogen is imported in the flask, heat up in a steamer the water that produces, be warming up to 220 ℃.
Confirm content in the flask become transparent after, decompression is heated up in a steamer and is anhydrated slowly.
Continue reaction, drop to below the 1KOHmg/g, obtain thus at polyester polyol A～G shown in 40 ℃ of tables 1 that are in a liquid state until the acid number of gained reaction solution.
As the rerum natura of gained polyester polyol A～G, measure its acid number, hydroxyl value, viscosity, zero pour and number-average molecular weight.The results are shown in Table 1.
Acid number, hydroxyl value, viscosity and zero pour are pressed JIS K 0070, JIS K 0070 respectively, JIS Z 8803, JISK 0065 measure.Number-average molecular weight is calculated by hydroxyl value.Table 1
Annotate) EG: ethylene glycol, 1,4-BD:1,4-butyleneglycol Production Example 2 (manufacturing of A composition 1～16)
| The kind of polyester polyol | ????A | ????B | ????C | ????D | ????E | ????F | ????G | |
| Aliphatics polyprotonic acid (weight part) | Hexanodioic acid (100) | Hexanodioic acid (100) | Hexanodioic acid (100) | Hexanodioic acid (100) | Hexanodioic acid (100) | Hexanodioic acid (100) | Hexanodioic acid (100) | |
| Aromatic series polyprotonic acid (weight part) | Terephthalic acid (12.6) | M-phthalic acid (12.6) | Phthalate anhydride (11.2) | Terephthalic acid (12.6) | ???- | Terephthalic acid (3.4) | Terephthalic acid (57.3) | |
| Aromatic/aliphatic polyprotonic acid (mol ratio) | 0.11 | ?0.11 | ?0.11 | ?0.11 | ???0 | ??0.03 | ?0.5 | |
| Polyvalent alcohol (weight part) | EG (51.1) | ?EG ?(51.1) | EG (51.1) | 1,4-BD (75.2) | ????EG ??(46) | ???EG ?(47.5) | ?EG (69) | |
| Rerum natura | Acid number (KOHmg/g) | 0.86 | ??0.63 | ?0.20 | ?0.77 | ??0.33 | ??0.51 | ?0.44 |
| Hydroxyl value (KOHmg/g) | 51.4 | ??50.1 | ?52.7 | ?50.4 | ??52.0 | ??51.3 | ?53.2 | |
| At 60 ℃ viscosity (mPas) | 1900 | ??2360 | ?2300 | ?2250 | ??1760 | ?1830 | ?13250 | |
| Zero pour (℃) | 25 | ??28 | ?25-28 | ?27 | ??19 | ?20 | ?57 | |
| Number-average molecular weight | 2147 | ??2240 | ?2130 | ??2186 | ??2154 | ?2183 | ?2105 | |
In four neck flasks, put into 4,4 ＇-diphenylmethanediisocyanate, adjust temperature to 60 ℃, load onto stirring rod, dehydrating tube, nitrogen ingress pipe and thermometer.
Then, in the vigorous stirring flask contents, any shown in the table 1 that will be obtained by Production Example 1 in nitrogen gas stream among polyester polyol A～G splashes in the flask slowly at 60 ℃, and temperature in the flask is remained on 60-70 ℃, reacts 2 hours.
Then, (Japanese Polyurethane Co., Ltd. product, trade(brand)name: CORONATE MX), recurring 1 hour obtains having the isocyanate composition of forming shown in the table 2 to add the MDI of carbodiimide modification in the flask.The rerum natura of gained isocyanate composition sees Table 2.
NCO% and viscosity press ASTM-D 1638-74 respectively and JIS Z 8803 measures.
The composition of A shown in the table 2 (isocyanate composition) 10 since the viscosity of polyester polyol G very high, can't splash at 40 ℃, therefore, be not mixed with.
Table 2
Annotate) EL-510: Asahi Glass Co., Ltd's product, trade(brand)name (number-average molecular weight 4000, average hydroxyl functional group several 2.0, the addition of end-rings oxidative ethane is arranged) EL-850: Asahi Glass Co., Ltd's product, trade(brand)name (number-average molecular weight 7000, average hydroxyl functional group several 3.0, the addition of end-rings oxidative ethane is arranged) PTMG-1000: Baotugu Chemical Industrial Co., Ltd's product, trade(brand)name (number-average molecular weight 1000, average hydroxyl functional group several 2.0, the addition of no end-rings oxidative ethane) PTMG-2000: Baotugu Chemical Industrial Co., Ltd's product, trade(brand)name (number-average molecular weight 2000, average hydroxyl functional group is several 2.0, the addition of no end-rings oxidative ethane) formulation example (preparation of B composition 1～3)
| The kind of A composition | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 | ????10 | ????11 | ????12 | ????13 | ????14 | ????15 | ????16 | |
| 4,4-diphenylmethanediisocyanate (weight part) | 100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | |
| Polyester polyol (weight part) | ???A ?37.1 | ???B ?37.1 | ??C ?37.1 | ??D ?37.1 | ??A ?53.4 | ??A ?35.9 | ??C ?37.1 | ??E ?37.1 | ??F ?37.1 | ??G ?37.1 | ??A ?54.0 | ??E ?37.1 | ??A ?78 | ??A ?34 | ??E ?78 | ??C ?54 | |
| Polyether polyol (weight part) | EL -510 ?18.5 | ?EL -510 ?18.5 | ?EL -510 ?18.5 | ?EL -510 ?18.5 | ?EL -510 ?26.7 | PTMG -2000 ?17.9 | ?EL -850 ?17.5 | ?EL -510 ?18.5 | ?EL -510 ?18.5 | ?EL -510 ?18.5 | ??- | ?EL -510 ?18.5 | ?-- | PTMG -1000 ???17 | ?- | ??- | |
| Polyester polyol/polyether polyol (weight ratio) | ?2/1 | ??2/1 | ??2/1 | ??2/1 | ?2/1 | ?2/1 | ??2/1 | ??2/1 | ??2/1 | ??2/1 | ??1/0 | ??2/1 | ??1/0 | ??2/1 | ??1/0 | ??1/0 | |
| Carbodiimide modification MDI (weight part) | ?25 | ??25 | ??25 | ??25 | ?25 | ?25 | ??25 | ??25 | ??25 | ??25 | ??25 | ?25 | ?25 | ?25 | ?25 | ?25 | |
| Rerum natura | NCO％ | ?21.6 | ??21.6 | ??21.6 | ??21.6 | ?18.6 | ?21.6 | ??21.6 | ??21.6 | ??21.6 | ??- | ??21.6 | ?18.5 | ?18.5 | ?21.6 | ?21.5 | ?21.6 |
| At 40 ℃ viscosity (mPas) | ?210 | ??225 | ??225 | ??220 | ?430 | ?220 | ??260 | ??195 | ??595 | ??- | ??245 | ?420 | ?550 | ?200 | ?235 | ?270 | |
Drop into the polyester polyol (starting monomer: ethylene glycol of the amount of Table 3, glycol ether and hexanodioic acid, ethylene glycol/glycol ether (mol ratio): 1/1, number-average molecular weight: 2200, average hydroxyl functional group number: 2), ethylene glycol (molecular weight: 62 as chain extension agent, hydroxy functional group number: 2), water as whipping agent, surfactant (siloxanes surfactant, Dow Chemical company product, trade(brand)name: DC-193), urethane catalysts (Kao Corp's product, AS-651-60C) and pigment (Union Chemical company product trade(brand)name:, trade(brand)name: P-505), adjust temperature to 40 ℃, stir, obtain B composition 1～3.The viscosity of gained B composition also is shown in table 3.
Viscosity is pressed JIS Z 8803 and is measured.Table 3
Embodiment 1-9
| The kind of B composition | ????1 | ????2 | ????3 | |
| The composition of B composition (weight part) | Polyester polyol | ????100 | ????100 | |
| Ethylene glycol (chain extension agent) | ????13 | ????15 | ????17 | |
| Water (whipping agent) | ????0.7 | ?????0.9 | ????1.15 | |
| Surfactant | ????0.5 | ?????0.5 | ????0.5 | |
| The urethane catalysts | ????1.5 | ?????1.5 | ????1.4 | |
| Pigment | ????5 | ????5 | ????5 | |
| Rerum natura | 40 ℃ (viscosity (mpas) | ????2300 | ????2100 | ????2000 |
In in the B composition 1～3 that will be obtained by formulation example any and the A composition 1～7 that obtained by Production Example 2 any drops into automatic mixed type shooting foaming machine (Polyurethane Engineering company product, pattern MU-203S, model 6-018) in, under following molding condition, foam, make the sole molding with urethane foam and the sole forming metal mould of 10mm * 100mm * 300mm.[molding condition]
Mixing temperature: the temperature of isocyanate prepolymer and polyol component all is adjusted to 35-45 ℃ of reactivity: livering time (cream time) 5-10 ST in second (string time) 15-30 (rise time) 35-60 tack-free time in second (tack free time) 30-55 molding in second that expands the time: 45-55 ℃ of release agent siloxanes of metal pattern temperature and wax density: free forming density 0.12-0.32g/cm in second3Slaking condition: next week of normal temperature [release property]
Be determined at time of making the demoulding of sole molding under the above-mentioned molding condition (not injured surface and shortest time of taking out).The results are shown in Table 4.
Then, as the final rerum natura of resulting sheet, measure the outward appearance of density, hardness, tensile strength (stretching resistance), elongation at break and the tearing strength and the sole molding of molding in order to following method.The results are shown in Table 4.[the final rerum natura of sheet material]
The density of molding: measure the weight of the urethane foam sheet material of 10mm * 100mm * 300mm,
Divided by volume 300cm
3After draw hardness (Asker C): measure tensile strength by SRIS 0101: with No. 1 dumbbell of JIS, measure elongations at break: with No. 1 dumbbell of JIS, by JISK 6301 mensuration tearing strengths: detect by an unaided eye by JIS K 7311 mensuration [outward appearance of sole molding], press following benchmark evaluation by JISK 6301
(A) metewand of surface pinholes
◎: do not have pin hole fully
Zero: the surface does not have pin hole basically
*: there is tangible pin hole or very many on the surface
(B) metewand of Shou Suoing
Zero: do not have and shrink
*: contraction is arranged
Table 4
Comparative example 1-10
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 | |
| Form | The kind of A composition | ????1 | ????2 | ????3 | ????4 | ????6 | ????7 | ????5 | ????3 | ????1 |
| The kind of B composition | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 | ????2 | ????3 | ????3 | |
| B composition/A composition (weight ratio) | 0.98 | ?0.98 | ?0.98 | ?0.98 | ?0.98 | ?0.98 | ?0.85 | ?0.80 | ?0.80 | |
| The demould time of sole molding (minute) | ???5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????7 | ????6 | ????6 | |
| Final rerum natura | Density (the g/cm of molding 3) | 0.42 | ?0.42 | ??0.42 | ?0.42 | ?0.42 | ?0.42 | ?0.42 | ?0.35 | ?0.35 |
| Hardness (AskerC) | ??80 | ???80 | ????79 | ???82 | ???82 | ???82 | ???80 | ???80 | ???80 | |
| Tensile strength (kgf/cm 2) | 55.8 | ?53.2 | ??53.9 | ?56.1 | ?55.3 | ?56.5 | ?54.6 | ?53.0 | ?53.5 | |
| Elongation at break (%) | ?420 | ??420 | ???440 | ??410 | ??420 | ??420 | ??430 | ??390 | ??390 | |
| Tearing strength (kgf/cm) | 26.1 | ?25.6 | ?25.6 | ?26.3 | ?26.0 | ?26.3 | ?25.8 | ?24.3 | ?24.8 | |
| Rerum natura | Surface pinholes | ○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?◎ | ○ | ?○ |
| Shrink | ○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | |
Except that using the A composition 8～9 or 11～16 that obtains by Production Example 2, by method making urethane foam sheet material and the sole molding same with embodiment 1-9.
By measuring the demould time of sole molding and the rerum natura and the sole molding outward appearance of gained urethane foam sheet material with the same method of embodiment 1-9.The results are shown in Table 5.Table 5
| Comparative example | ????1 | ????2 | ?????3 | ?????4 | ?????5 | ?????6 | ?????7 | ????8 | ????9 | ????10 | |
| Form | The kind of A composition | ????8 | ????9 | ????11 | ????14 | ????12 | ????13 | ????15 | ????8 | ????16 | ????11 |
| The kind of B composition | ????1 | ????1 | ????1 | ????1 | ????2 | ????2 | ????1 | ????3 | ????3 | ????3 | |
| B composition/A composition (weight ratio) | 0.98 | ?0.98 | ?0.98 | ?0.98 | ?0.85 | ?0.85 | ?0.98 | ?0.98 | ?0.98 | ?0.98 | |
| The demould time of sole molding (minute) | 9 | ?8.5 | ?5 | ?9 | ?12 | ?9 | ?9 | ?10 | ?9 | ?9 | |
| Final rerum natura | Density (the g/cm of molding 3) | 0.42 | ?0.42 | ?0.42 | ?0.42 | ?0.85 | ?0.85 | ?0.42 | ?0.35 | ?0.35 | ?0.35 |
| Hardness (AskerC) | 76 | ?76 | ?85 | ?84 | ?76 | ?82 | ?76 | ?76 | ?79 | ?76 | |
| Tensile strength (kgf/cm 2) | 46.6 | ?47.3 | ?57.7 | ?57.2 | ?49.2 | ?56.2 | ?48.4 | ?45.5 | ?49.5 | ?50.4 | |
| Elongation at break (%) | 430 | ?400 | ?420 | ?410 | ?410 | ?420 | ?380 | ?380 | ?370 | ?370 | |
| Tearing strength (kgf/cm) | 20.5 | ?21.3 | ?27.2 | ?26.1 | ?19.9 | ?27.3 | ?19.5 | ?19.3 | ?20.1 | ?20.5 | |
| Rerum natura | Surface pinholes | ○ | ?○ | × | × | ○ | × | × | ○ | × | × |
| Shrink | ○ | ?○ | × | × | ○ | × | × | ○ | × | × | |
According to above result, embodiment and comparative example are investigated.
In embodiment 1, do not compare with 2 situation with do not contain the low comparative example 1 of aromatic series polyprotonic acid or its content at the polyester polyol that is used for the A composition, the demould time of sole molding can be shortened, and on final rerum natura, tensile strength etc. can be significantly improved.
In embodiment 2-4,, still can obtain sufficient release property and improve final rerum natura and improve outward appearance even find to change the kind of aromatic series polyprotonic acid of the polyester polyol that is used for the A composition or the kind of polyvalent alcohol.
In embodiment 5 and 6, find that the kind or the average hydroxyl functional group number of the polyether polyol that uses in the A composition is different with embodiment 1, but still can obtain sufficient release property and improve final rerum natura and improve outward appearance.
The embodiment 1 that contains polyether polyol in the A composition compares with the comparative example 3 that does not contain polyether polyol, and the molding surface does not have pin hole and contraction, has good surface appearance.
Embodiment 5 with reduced the A composition in the comparative example 4 of molecular weight of the polyether polyol that uses compare, pin hole and contraction are not seen in the molding surface, have good surface appearance.
Embodiment 7 and comparative example 5 and 6 have reduced the NCO% of A composition, and embodiment 7 compares with comparative example 5, has good release property and rerum natura, compare with comparative example 6, have good surface appearance.Especially pin hole is not seen on the surface of embodiment 7 fully.
Do not contain the aromatic series polyprotonic acid and do not use in the comparative example 7 of polyether polyol the shortcoming of exist sole demould time length, poor properties, molding surface that many pin holes are arranged, contraction to occur, the molding outward appearance is not good enough yet at the polyester polyol that is used for the A composition.
It is 0.35g/cm that embodiment 8-9 and comparative example 8-10 are mixed with molding density
3Compare with the comparative example 8 that does not contain the aromatic series polyprotonic acid in the used A composition (isocyanate composition), embodiment 8 has good hardness and various intensity.In addition, compare with the comparative example 9-10 that does not contain polyether polyol in the used A composition (isocyanate composition), pin hole and contraction are not observed in the molding surface of embodiment 8-9, and outward appearance is good, various physical properties excellent.
The possibility of utilizing on the industry
Manufacturing method according to the invention can shorten the demould time of formed body, boosts productivity.
In addition, manufacturing method according to the invention, the polyurethane foam plastics that can obtain the formed body surface and do not have pin hole and contraction etc., have the final physical property such as good hot strength.
Therefore, the polyurethane foam plastics that obtains with manufacture method of the present invention is suitable as sole with polyurethane foam plastics etc.
Claims (5)
1. the manufacture method of urethane foam, it comprises following A composition and the reaction of B composition:
The A composition: isocyanate composition, it contains mol ratio by aromatic series polyprotonic acid/aliphatics polyprotonic acid is the polyprotonic acid composition of 0.05-0.4 and polyester polyol that the polyhydroxy reactant polycondensation obtains and is that 2-6 and number-average molecular weight are that to react the end that obtains with organic multiple isocyanate be the prepolymer of isocyanic ester for the polyether polyol of 1500-20000 by average hydroxyl functional group number;
The B composition: polyhydroxy reactant, it contains polyester polyol or polyether polyol, chain extension agent, whipping agent, urethane catalysts.
2. the manufacture method of urethane as claimed in claim 1, wherein, the average hydroxyl functional group number of polyester polyol that uses in the described B composition or polyether polyol is 2-6, number-average molecular weight is 500-6000.
3. the manufacture method of urethane foam as claimed in claim 1 or 2, wherein, to be the hydroxy functional group number be 2-6, the molecular weight polyvalent alcohol as 62-499 to the chain extension agent that uses in the described B composition.
4. as the manufacture method of each described urethane foam among the claim 1-3, wherein, the amount of the chain extension agent that uses in the described B composition is equivalent to the 2-30 weight % of polyester polyol or polyether polyol.
5. as the manufacture method of each described urethane foam among the claim 1-4, wherein, the NCO% of described isocyanate composition is 15-25 weight %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP175088/1998 | 1998-06-22 | ||
| JP17508898 | 1998-06-22 |
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| Publication Number | Publication Date |
|---|---|
| CN1306549A true CN1306549A (en) | 2001-08-01 |
| CN1122058C CN1122058C (en) | 2003-09-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99807536 Expired - Fee Related CN1122058C (en) | 1998-06-22 | 1999-06-21 | Process for producing polyurethane foamed plastic |
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| Country | Link |
|---|---|
| JP (1) | JP3589423B2 (en) |
| CN (1) | CN1122058C (en) |
| ID (1) | ID28836A (en) |
| MY (1) | MY128201A (en) |
| WO (1) | WO1999067313A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058629B (en) * | 2006-04-19 | 2010-11-17 | 日本聚氨酯工业株式会社 | Foaming polyurethanes elastomer, manufacturing method thereof and pallet for railway |
| CN102504181A (en) * | 2011-09-30 | 2012-06-20 | 无锡双象化学工业有限公司 | Resin used for polyurethane cold-resistant flexible middle/low-density shoes and preparation method thereof |
| CN107922560A (en) * | 2015-08-18 | 2018-04-17 | 三井化学株式会社 | The manufacture method of blown polyurethane materials, products formed and blown polyurethane materials |
| CN109627746A (en) * | 2018-11-23 | 2019-04-16 | 贵州航天天马机电科技有限公司 | A kind of frangible formula protection cap in big negative pressure polyurethane front end and its forming method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8819759D0 (en) * | 1988-08-19 | 1988-09-21 | Ici Plc | Novel prepolymer compositions |
| IT1240635B (en) * | 1990-05-04 | 1993-12-17 | Dow Italia | MICROCELLULAR POLYURETHANE POLYMERS PREPARED FROM THREE POLY POLYMERS (TETRAMETHYLENE) GLYCOLS WITH ISOCYANATE GROUPS TERMINALS |
| JP2583155B2 (en) * | 1990-11-21 | 1997-02-19 | 日本ポリウレタン工業株式会社 | Method for producing flexible polyurethane foam |
| GB9216631D0 (en) * | 1992-08-05 | 1992-09-16 | Ici Plc | Reaction system for preparing microcellular elastomers |
| JP3100349B2 (en) * | 1996-03-12 | 2000-10-16 | 花王株式会社 | Method for producing polyurethane foam |
-
1999
- 1999-06-21 JP JP2000555961A patent/JP3589423B2/en not_active Expired - Fee Related
- 1999-06-21 MY MYPI9902549 patent/MY128201A/en unknown
- 1999-06-21 WO PCT/JP1999/003296 patent/WO1999067313A1/en active Application Filing
- 1999-06-21 CN CN 99807536 patent/CN1122058C/en not_active Expired - Fee Related
- 1999-06-21 ID IDW20002592A patent/ID28836A/en unknown
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058629B (en) * | 2006-04-19 | 2010-11-17 | 日本聚氨酯工业株式会社 | Foaming polyurethanes elastomer, manufacturing method thereof and pallet for railway |
| CN102504181A (en) * | 2011-09-30 | 2012-06-20 | 无锡双象化学工业有限公司 | Resin used for polyurethane cold-resistant flexible middle/low-density shoes and preparation method thereof |
| CN102504181B (en) * | 2011-09-30 | 2014-05-07 | 无锡双象化学工业有限公司 | Resin used for polyurethane cold-resistant flexible middle/low-density shoes and preparation method thereof |
| CN107922560A (en) * | 2015-08-18 | 2018-04-17 | 三井化学株式会社 | The manufacture method of blown polyurethane materials, products formed and blown polyurethane materials |
| CN107922560B (en) * | 2015-08-18 | 2019-04-05 | 三井化学株式会社 | The manufacturing method of blown polyurethane materials, molded product and blown polyurethane materials |
| US10513575B2 (en) | 2015-08-18 | 2019-12-24 | Mitsui Chemicals, Inc. | Foam polyurethane material, molded article, and method for producing foam polyurethane material |
| CN109627746A (en) * | 2018-11-23 | 2019-04-16 | 贵州航天天马机电科技有限公司 | A kind of frangible formula protection cap in big negative pressure polyurethane front end and its forming method |
| CN109627746B (en) * | 2018-11-23 | 2021-04-06 | 贵州航天天马机电科技有限公司 | Large negative pressure polyurethane front end fragile protective cover and forming method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3589423B2 (en) | 2004-11-17 |
| CN1122058C (en) | 2003-09-24 |
| WO1999067313A1 (en) | 1999-12-29 |
| ID28836A (en) | 2001-07-05 |
| MY128201A (en) | 2007-01-31 |
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