CN1506395A - Prepn of laminated silicate modified fireproof hard foamed polyurethane - Google Patents
Prepn of laminated silicate modified fireproof hard foamed polyurethane Download PDFInfo
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Abstract
The preparation process of laminated silicate modified fireproof hard foamed polyurethane includes the following steps: mixing multi-hydroxyl compound, catalyst, foam stabilizer, fire retardant and other components homogeneously to prepare polyurethane composition; forced mixing the polyurethane composition with surface treated laminated nano silicate at 30-50 deg.c for at least 30 min to operate intercalated mixture; mixing the intercalated mixture with foaming agent at 15-25 deg.c and further mixing with polyisocyanate to produce intercalation reaction resulting in hard foamed PU material with excellent fireproof and mechanical performance. Without the plasticizing effect of organic phospine fire retardant and hydrofluochlorohydrocarbon in foamed PU, the hard foamed PU material of the present invention has excellent fireproof performance as well as high compression strength and high size stability.
Description
1. background of invention
The present invention relates to a kind of method for preparing the high flame retardant hard polyurethane foam.
Urethane (PU) hard bubbles and has good heat insulation and physical and mechanical properties, in pipelines and petrochemical pipelines, is used widely on refrigerating plant and the buildings.The PU that is generally used for building hard bubbles needs higher flame retardant resistance.PU hard bubbles normally in the presence of whipping agent, and polyisocyanates and polyol blends reaction are made.Because PU hard bubbles and is unicellular structure, contains certain amount of foaming agent in the micropore of sealing usually, the flame retardant properties of whipping agent has direct influence to final PU foamy fire line.Traditional freonll-11 (CFCs) has advantage such as do not burn, the steam heat conductance is low, can give PU the excellent comprehensive performances of hard bubbling, and still, CFC has a fatal problem-meeting to destroy the ozonosphere of earth atmosphere, thereby its application is subjected to great restriction.Closely during the last ten years, the exploitation of CFC substitute and auxiliary products thereof is a PU industry important research project always.Hydrogen fluorohydrocarbon (HFCs such as HFC-245fa) and hydrocarbon compound (HCs) are considered to ozonosphere is not had the whipping agent (depletion of the ozone layer dive value ODP=0) of destruction, are most promising whipping agents in the 21 century PU foam.But this two classes whipping agent belongs to inflammable substance, when preparation high flame retardant PU hard bubbles, when using HFC and hydrocarbons, has increased the difficulty of flame-retarded technology.
With the ODP value be zero or the whipping agent of low ODP value prepare existing report of patent that PU hard bubbles, USP5496866 for example, USP4379706, USP5430071, USP5444101 etc.
Adopt the inflammableness whipping agent to prepare the problem that high flame retardant PU hard bubbles for solving, European patent EP 0394769A has disclosed the employing pentamethylene and has prepared fire-retardant PU foamy method as whipping agent.The fire retardant that this method adopts is that polyphosphoric acid amine and dimethyl phosphonic acids methyl esters (DMMP) collocation are used.USP5556894 has disclosed with pentamethylene and has made whipping agent, as auxiliary blowing agent, adopts isocyanurate-modified and nitrogenous polyvalent alcohol bonded technological line to prepare flame-retardant rigid-foam with the small molecules fat alkane that contains the second month in a season or uncle's chlorine.The disclosed PU of USP5776992 (1998) hard bubble flame resistant method be will contain the polyethers and the polyisocyanates reaction of N element, as fire retardant, prepared foam flame retardant resistance reaches the B2 level of DIN4102 testing method with polyphosphoric acid amine.The PU that U.S. Pat P6372811 (2002) discloses hard bubbles the flame-retarded technology route for using aromatic polyester polyvalent alcohol and isocyanate reaction, adopt organic phosphine fire retardant TEP and freonll-11 substitute HFC-245fa, gained foam flame retardant properties (Butler test) is as follows: weight retention rate 90%, flame height: 24cm, fray-out of flame time: 18s, smoke density: 84.The used organic phosphine fire retardant of this patent also has DMMP, tributyl phosphate (TBP) etc., and used whipping agent also can be HCFC-141b.
Adding fire retardant is a kind of main method of preparation flame retardant resistance PU foamy.Fire retardant commonly used is halogen-containing and P contained compound.Have smoke density and the big shortcoming of toxicity with the fire-retardant foam of halogen contained compound; Though the PU foam smoke density fire-retardant with P contained compound is lower, and be stronger to the foamy plastification, can bring adverse influence to the performance of material.In addition, as transition scheme, use more whipping agent to be HCFC-141b in recent years, with the CFCs ratio, 141b has stronger polarity, and the solubleness in the PU foam is bigger, cause foam base plate softening, the supporting role of abscess is reduced, cause the dimensional stability variation.
The objective of the invention is to develop a kind of with the ODP value be zero or the whipping agent (HFCs, HCFCs and HCs) of low ODP value prepare the method that fire-retardant PU hard bubbles.Prepared PU hard bubbles and can overcome the organic phosphine fire retardant and the solubleness of hydrogen fluorochlorohydrocarbon (as HCFC-141b) in the PU foam is bigger, cause foam base plate softening, the shortcoming of dimensional stability variation, and good flame-retardant effect is arranged is to satisfy building trade to the hard bubble requirement of high flame retardant of PU.
2. detailed Description Of The Invention
The present invention adopts the phyllosilicate nano material to coat the technological line that combines with traditional flame resistant method.
A large amount of researchs show, the particle of nano-scale (1-100nm) have with macroscopic particles different special volume effect (small-size effect), interfacial effect and macro quanta tunnel effect etc., thereby show particular performances, for preparation high-performance multifunctional composite has been opened up a brand-brand-new way.Since the nineties in 20th century, nanotechnology is applied to the modification of polymkeric substance, in recent years, the research of a small amount of bibliographical information nano modification polyurethane elastomer is arranged, but does not see the research report that is useful on the foam modification so far as yet.
The present invention adopts the silicate nano material with special two-dimensional layered structure, its two-dimensional is generally the laminate chemical constitution of 20 * 60nm layered silicate, interlayer ion kind and quantity, interlamellar spacing and grain-size and distribution thereof have controllability. utilize its special two-dimensional layered structure and huge surface-area thereby polyvalent alcohol and isocyanic ester can be carried out intercalation polyaddition reaction formation nano-polyurethane matrix material between laminate. and the distinctive nano effect of layered silicate makes prepared PU foam have excellent physicals, its huge surface-area is coated on the PU matrix surface, PU foam oxide side is reduced, can improve its flame retardant resistance, and the supportive of PU foam base plate is strengthened, thereby overcome the shortcoming that causes the foam base plate deliquescing by 141b whipping agent and organic phosphine fire retardant.
The present invention is raw materials used as follows:
(a) polyester or polyether glycol. suitable polyether glycol is generally poly(propylene oxide) (PPO) type, its initiator can be a glycerine, quadrol, Diethylene Glycol, sorbyl alcohol, sucrose or its mixture etc. GQ835 for example, GSU-450L (Shanghai Gaoqiao petrochemical industry three factories), TSU450L, TPE450 (Plant of Tianjin Petrochemical Company three factories). polyether glycol also can be to contain ignition-proof element (halogen, nitrogen, phosphorus) polyethers, PHT-4 for example, AMGARD V82, IXOL B251 (SOLVAYFLUOR AND DERIVATE GmbH). the polyester polyol that is suitable for is generally the polyester that contains aromatic ring structure, its functionality is to be made by polycondensation by polycarboxylic acid or acid anhydrides and polyol less than 3. this polyester usually, used carboxylic acid can be the mixture of aliphatics and aromatic carboxylic acid, but should have a kind of at least is the carboxylic acid that contains aromatic nucleus. PS3152 for example, PS-2412, PS-2352 (STEPAN COMPANY), ISOEXTER 3061,4537 (COIM COMPANY) etc. the hydroxyl value of used polyvalent alcohol is 100-800mgKOH/g, is preferably 150-450mg KOH/g.
(b) catalyzer. the used catalyzer of the present invention comprises polyurethane reaction and poly-isocyanurate catalyst for reaction. the catalyzer that is used for polyurethane reaction comprises aminated compounds and organometallic compound. pentamethyl-diethyl triamine (Polycat 5) for example, dimethylcyclohexylamine (DMCHA), N-methylmorpholine, vegolysen, 3,5-triazine-1,3,5-tripropyl amine (Polycat 41), dimethylethanolamine (DMEA), dibutyl tin laurate, dibutyltin diacetate etc. being used for the poly-isocyanurate catalyst for reaction has alkali metal carboxylate usually, isocaprylic acid potassium for example, potassium acetate, 2 ethyl hexanoic acid potassium (K-15) etc.; Own ammonium salt is as Dabco TMR, TMR-2; N, N ', N " the symmetrical Hexahydrotriazine of-three (dimethylaminopropyl), 2,4,6-three (dimethylamino methyl) phenol.
(c) whipping agent. the used whipping agent of the present invention is the whipping agent that the latent value (ODP) of depletion of the ozone layer is zero or low ODP value, as the hydrogen fluorochlorohydrocarbon, the hydrogen fluorohydrocarbon, low molecule alkane etc. the whipping agent that is suitable for has dichloro one fluoroethane (HCFC-141b), dichlorotrifluoroethane (HCFC-123); 1,1,1-Halothane, 1,4-hexafluoro butane (HFC-356mffm), 1,3-3-pentafluorobutane (HFC-365mfc), 1,4-3-pentafluorobutane (HFC-245fa); Skellysolve A, iso-pentane, pentamethylene etc.Water can generate carbon dioxide with isocyanate reaction, thereby, also can adopt water as whipping agent among the present invention.Usually water is mixed use with other whipping agents.
(d) organic phosphine compound.Organic phosphorus compound can be used as fire retardant.P contained compound commonly used has: phosphoric acid ester, phosphorous acid ester, polyphosphate, poly phosphorous acid ester, ammonium polyphosphate.The organic phosphine fire retardant that is suitable for has: methyl-phosphoric acid dimethyl ester (DMMP), diethyl ethylphosphate (DEEP), ammonium polyphosphate (APP), phosphonic acids triethyl (TEP), phosphonic acids tri-n-butyl (TBP) etc.The consumption of organophosphorous fire retardant is generally the 10-40% of polyvalent alcohol, is preferably 15-25%.
(e) layered silicate.Layered silicate used in the present invention is the polynite through surface chemical modification, hydrotalcite.Polynite through the organic cation modification is best.Its consumption is generally the 3-15% of polyvalent alcohol consumption, is preferably 4-8%.
(f) isocyanic ester.Isocyanic ester used in the present invention is many phenylmethanes polyisocyanates (p-MDI) and modification body thereof. SUP5005 for example, SUP2085 (HUNTSMAN CORP.), M20S (BASF CORP.) 44V20 (BAYER CORP.), PM-200 (. the magnificent urethane in Yantai ten thousand company) etc. the 1.5-4 that the consumption of polyisocyanates is generally the polyvalent alcohol consumption doubly is preferably 2-3 doubly.
(g) suds-stabilizing agent and additive.Suds-stabilizing agent used in the present invention can be various hard polyurethane foam or the polymeric polyisocyanate foamy tensio-active agents of being used for. B8404 for example, B8460, B8462 (German Gauss Mitt USA Corporation); L-6900, L-5440, L-5420, L-5421 (U.S. Compton Co.,Ltd); DC5604, DC193, DC5589, DC5103 (U.S. gas products company) etc.
When the preparation hard polyurethane foam, can add additives such as mill base, anti-aging agent as required. implementation step of the present invention is described as follows:
(1) with polyol (polyethers or polyester polyol), catalyzer, components such as suds-stabilizing agent and fire retardant mix, and make polyurethane combined material (I).
(2) with I and surface treated layered nano silicate powerful mixing at least 30 minutes under 30-50 ℃ of temperature, obtain intercalation mixture (II).
(3) II and whipping agent are mixed under 15-25 ℃, mix with polyisocyanates again, make it that intercalation polymeric reaction take place, make the good PU rigid foam of flame retardant resistance and physical and mechanical properties.
By the flame-retardant foam that the present invention makes, can be used for making air conditioning wind pipe sheet material, heat-insulating sheet material, piping insulation etc. the preparation process of flame-retardant foam is exemplified below:
Used starting material are described as follows in the example:
Stepanol 3152 contains the polyester polyol of aromatic nucleus, hydroxyl value: 320mgKOH/g
Terate 204 contains the polyester polyol of aromatic nucleus, hydroxyl value: 275mgKOH/g
The B-8806 suds-stabilizing agent.
The DC-193 suds-stabilizing agent, U.S. gas products company.
The HCFC-141 whipping agent
The pentamethylene whipping agent
Polycat 5 catalyzer, U.S. gas products company.
Dabco K-15 catalyzer, U.S. gas products company.
The DMMP fire retardant, the sincere chemical industry in sky, Zhejiang company limited
The DEEP fire retardant,
TJ-2 organic cation modified sheet silicate.Beijing nanometer scientific ﹠ technical corporation of connection section.
PM-200 polymethylene polyisocyanates. the magnificent urethane in Yantai ten thousand company.
Example 1
Press the prescription of the listed sample 1 of table 1, with polyvalent alcohol, suds-stabilizing agent, catalyzer, after fire retardants etc. accurately measure, mix and obtain polyurethane combined material. keep temperature of charge about 45 ℃, this polyurethane combined material and layered silicate mixed in decollator obtained the intercalation mixture in 40 minutes. after being cooled to 15-25 ℃, the intercalation mixture adds whipping agent, with the material thorough mixing evenly after, give birth to reaction with the polyisocyanates hybrid concurrency and generate the high flame retardant polyurethane foam. reaction mass is poured in the mould of 100*25*2cm, make the free foaming sample respectively, fill 20% molding sample excessively.The molding sample is tested its flame retardant resistance by GB GB8624-1997.
Example 2-5
Press the prescription of the listed sample 2-5 of table 1, technological process is with example 1.Example 2-4 is under the condition of using layered silicate, the foam that whipping agent, polyvalent alcohol, suds-stabilizing agent and the fire retardant in filling a prescription by change makes.
Example 6-8
Press the prescription of the listed sample 6-8 of table 1, technological process is with example 1.Comparison example when example 6-8 is no layered silicate.With compare with lamella silicate modified foam, these foamy ultimate compression strength and dimensional stability and flame retardant resistance are relatively poor.
The prescription of table 1. resistance combustion polyurethane foam and performance.
| Example | 1???????2???????3???????4??????5??????6??????7??????8 |
| Prescription Stepanol 3152 Terate 204 B8806 DC-193 Polycat 5 K-15 Water DMMP DEEP TJ-2 HCFC-141b HFC-245fa pentamethylene Suprasec2085 | 100?????100?????????????50?????70?????50?????70 ????????????????100?????50?????30?????50?????30?????100 2.??????2???????2??????????????2?????????????2??????2 ????????????????????????2?????????????2 0.5?????0.5?????0.5?????0.5????0.5????0.5????0.5????0.5 2.5?????2.5?????2.5?????2.5????2.5????2.5????2.5????2.5 1.0?????1.0?????1.0?????1.0????1.0????1.0????1.0????1.0 25??????25??????30??????25????????????25????????????30 ???????????????????????????????20????????????20 7???????7???????5???????5??????5??????-??????-??????- 30??????????????????????30?????30?????30?????30 ????????35 ????????????????14??????????????????????????????????14 302?????302?????300?????305????300????304????300????302 |
| Performance: freely steep density, kg/m 3Molding density, kg/m 3Compressive strength, the kpa dimensional stability, the % flame retardant resistance: | ? 42??????40??????39.5????41?????42?????42?????42?????41.5 ? 51??????52??????50??????50?????52?????52?????52?????52 ? 234?????240?????245?????243????247????212????203????224 ? 0.5?????0.45????0.5?????0.4????0.4????0.8????0.8????0.7 ? B1??????B1??????B1??????B1?????B1?????B1?????B2?????B2 |
Claims (8)
1. the preparation method of lamella silicate modified high flame-retardant polyurethane rigid foam is characterized in that:
(1) with polyol (polyethers or polyester polyol), catalyzer, components such as suds-stabilizing agent and fire retardant mix, and make polyurethane combined material (I).
(2) with I and surface treated layered nano silicate powerful mixing at least 30 minutes under 30-50 ℃ of temperature, obtain intercalation mixture (II).
(3) II and whipping agent are mixed under 10-25 ℃, mix with polyisocyanates again, make it that intercalation polymeric reaction take place, make the good PU rigid foam of flame retardant resistance and physical and mechanical properties.
2. the method for preparing the high flame retardant hard polyurethane foam according to claim 1 is characterized in that used fire retardant is an organo phosphorous compounds, comprises phosphoric acid ester, phosphorous acid ester, polyphosphate, poly phosphorous acid ester and ammonium polyphosphate.
3. the method for preparing the high flame retardant hard polyurethane foam according to claim 1 is characterized in that used layered nano silicate is the polynite through surface chemical modification, hydrotalcite etc.
4. the method for preparing the high flame retardant hard polyurethane foam according to claim 1, the processing condition that it is characterized in that preparing the intercalation mixture are powerful mixing under 30-50 ℃ of temperature at least 30 minutes.
5. the method for preparing the high flame retardant hard polyurethane foam according to claim 1 is characterized in that used whipping agent is the hydrogen fluorohydrocarbon (HFC) that the latent value (ODP) of depletion of the ozone layer is zero or low ODP value, hydrogen fluorochlorohydrocarbon (HCFC) and alkane compound.
6. according to claim 1, the 2 described methods that prepare the high flame retardant hard polyurethane foam, it is characterized in that used organophosphorous fire retardant consumption is the 10-40% of polyvalent alcohol consumption.
7. according to claim 1, the 3 described methods that prepare the high flame retardant hard polyurethane foam, it is characterized in that used layered silicate consumption is the 3-10% of polyvalent alcohol consumption.
8. according to claim 1,2,3,4,5,6, the 7 described methods that prepare the high flame retardant hard polyurethane foam, it is characterized in that used polyisocyanates consumption is 1.5-4 a times of polyvalent alcohol consumption.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100376632C (en) * | 2004-08-24 | 2008-03-26 | 邱连生 | Nanometer montmorillonite-soft polyurethane foam plastic and its prepn process |
| CN100434471C (en) * | 2005-07-27 | 2008-11-19 | 北京绿寰宇化工有限公司 | Production method of nanometer material modified toughened melamine foamed plastic |
| CN101177525B (en) * | 2006-11-08 | 2010-05-12 | 上海昊海化工有限公司 | Fibre-reinforced polyurethane modified polyisocyanurate composite material and preparation method thereof |
| CN102391465A (en) * | 2011-09-14 | 2012-03-28 | 可利亚多元醇（南京）有限公司 | Highly flame-retardant plate polyisocyanurate composite material and preparation method thereof |
| CN102786650A (en) * | 2012-07-12 | 2012-11-21 | 烟台万华聚氨酯股份有限公司 | Stably foamed polyisocyanurate foam material and its preparation method |
| CN103030780A (en) * | 2012-12-31 | 2013-04-10 | 南京弘诺科技有限公司 | Flame-retardant polyurethane modified polyisocyanurate foam, and preparation method and application of foam |
| CN104086878A (en) * | 2014-06-30 | 2014-10-08 | 邹玲姣 | Fire retardant composition |
| CN105330818A (en) * | 2015-12-01 | 2016-02-17 | 中国科学技术大学苏州研究院 | Flame retardant rigid polyurethane foam material and preparation method thereof |
| CN105713166A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Hard polyurethane foam containing organic-inorganic hybrid material and preparation method thereof |
| CN108130652A (en) * | 2016-12-01 | 2018-06-08 | 北京泰洋泉生物科技有限公司 | A kind of polylactic acid non-woven fabrics and preparation method and application |
| CN108973268A (en) * | 2018-06-29 | 2018-12-11 | 南京红宝丽新材料有限公司 | A kind of building heat preservation hardfaced plate and preparation method thereof |
| CN109219634A (en) * | 2016-05-24 | 2019-01-15 | 科莱恩国际有限公司 | Improve the antisticking component of the anti-adhesive property of thermoplastic package material |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376632C (en) * | 2004-08-24 | 2008-03-26 | 邱连生 | Nanometer montmorillonite-soft polyurethane foam plastic and its prepn process |
| CN100434471C (en) * | 2005-07-27 | 2008-11-19 | 北京绿寰宇化工有限公司 | Production method of nanometer material modified toughened melamine foamed plastic |
| CN101177525B (en) * | 2006-11-08 | 2010-05-12 | 上海昊海化工有限公司 | Fibre-reinforced polyurethane modified polyisocyanurate composite material and preparation method thereof |
| CN102391465B (en) * | 2011-09-14 | 2013-04-17 | 可利亚多元醇（南京）有限公司 | Highly flame-retardant plate polyisocyanurate composite material and preparation method thereof |
| CN102391465A (en) * | 2011-09-14 | 2012-03-28 | 可利亚多元醇（南京）有限公司 | Highly flame-retardant plate polyisocyanurate composite material and preparation method thereof |
| CN102786650A (en) * | 2012-07-12 | 2012-11-21 | 烟台万华聚氨酯股份有限公司 | Stably foamed polyisocyanurate foam material and its preparation method |
| CN103030780A (en) * | 2012-12-31 | 2013-04-10 | 南京弘诺科技有限公司 | Flame-retardant polyurethane modified polyisocyanurate foam, and preparation method and application of foam |
| CN104086878A (en) * | 2014-06-30 | 2014-10-08 | 邹玲姣 | Fire retardant composition |
| CN105713166A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Hard polyurethane foam containing organic-inorganic hybrid material and preparation method thereof |
| CN105330818A (en) * | 2015-12-01 | 2016-02-17 | 中国科学技术大学苏州研究院 | Flame retardant rigid polyurethane foam material and preparation method thereof |
| CN105330818B (en) * | 2015-12-01 | 2018-05-04 | 中国科学技术大学苏州研究院 | A kind of flame retardant polyurethane rigid foam material and preparation method thereof |
| CN109219634A (en) * | 2016-05-24 | 2019-01-15 | 科莱恩国际有限公司 | Improve the antisticking component of the anti-adhesive property of thermoplastic package material |
| CN108130652A (en) * | 2016-12-01 | 2018-06-08 | 北京泰洋泉生物科技有限公司 | A kind of polylactic acid non-woven fabrics and preparation method and application |
| CN108973268A (en) * | 2018-06-29 | 2018-12-11 | 南京红宝丽新材料有限公司 | A kind of building heat preservation hardfaced plate and preparation method thereof |
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Owner name: SHANGHAI WUHAI CHEMICAL CO., LTD.; SHANGHAI LIANH Free format text: FORMER OWNER: SHANGHAI WUHAI CHEMICAL CO., LTD. Effective date: 20080926 |
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Effective date of registration: 20080926 Address after: No. 2, 139 Anshun Road, Shanghai, building 5, post code: 200052 Co-patentee after: Shanghai Union Inhalator Products Canned Co., Ltd. Patentee after: Shanghai Hao Hai Chemical Co., Ltd. Address before: C, building 5, 1366 triumphal road, Shanghai, 200052 Patentee before: Shanghai Wuhai Chemical Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060308 Termination date: 20191211 |