CN1986593A - Hard polyurethane foam composition with fast demolding performace - Google Patents
Hard polyurethane foam composition with fast demolding performace Download PDFInfo
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- CN1986593A CN1986593A CN 200610041382 CN200610041382A CN1986593A CN 1986593 A CN1986593 A CN 1986593A CN 200610041382 CN200610041382 CN 200610041382 CN 200610041382 A CN200610041382 A CN 200610041382A CN 1986593 A CN1986593 A CN 1986593A
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- polyurethane foam
- polyethers
- addition reaction
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- olefin oxide
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Abstract
The hard polyurethane foam composition with fast demolding performance consists of: composite polyether 100 weight portions comprising polyether prepared with cane sugar and olefin oxide through addition reaction 30-60 weight portions, polyether prepared with sorbic alcohol and olefin oxide through addition reaction 5-25 weight portions, polyether prepared with toluene diamine, triisopropanolamine and olefin oxide through addition reaction 15-30 weight portions, and polyether prepared with glycerin and olefin oxide through addition reaction 5-20 weight portions; composite catalyst 1.6-3.3 weight portions; foaming agent 7-16 weight portions; water 1.5-3.0 weight portions; foam stabilizer 1.4-4.0 weight portions; and isocyanate polymer 95-150 weight portions. The present invention has excellent flowability, fast demolding performance, excellent mechanical performance and high size stability.
Description
Technical field
The present invention relates to the hard polyurethane foam component in a kind of organic chemistry filed, particularly relate to a kind of hard polyurethane foam component that has good demoulding property.
Background technology
Hard polyurethane foams is under the existence of catalyzer, whipping agent and suds-stabilizing agent etc. and effect, by-OH and-NCO reacts to each other and is prepared from, its thermal conductivity in all thermal insulation materials is minimum, heat-insulating property is best, so it is widely used in the thermal insulating warm-keeping layer of refrigerator, refrigerator, freezer plate, sandwich panel, piping insulation, thermal container etc.But along with banning use of of fluorine Lyons, the restriction of HCFC-141b is used, the pentane-blown technology is to adopt the foaming technique of maximum usefulness at present in the world, also is the foaming technique that people more and more recommend and adopt hydrogen fluorohydrocarbon such as HFC-245fa and HFC-365mfc/227ea to make whipping agent.
Concerning the producer, the production cycle that shortens product is the direction of making great efforts always, and the required demould time of polyurethane foam is the principal element that influences polyurethane products production efficiency.
For a long time, the material supplier is for improving the competitive edge of raw material, be devoted to develop the hard polyurethane foam component of accelerating demould time, the report that this respect is just arranged as relevant document and patent CN02120940.5, but they only are improvement based on HCFC-141b foaming system or demolding performace only, and do not have clear and definite concrete demould time.
Summary of the invention
Technical problem underlying to be solved by this invention be exactly the required demould time of existing polyurethane foam be the problem that influences polyurethane products production efficiency, a kind of fast demolding performace hard polyurethane foam component that has is provided, can prepares the low hard polyurethane foams of foaming after rate.
The present invention includes following moiety:
(a) with sucrose as initiator by with resulting polyethers 30～60 weight parts of the addition reaction of olefin oxide; With sorbic alcohol as initiator by with resulting polyethers 5～25 weight parts of the addition reaction of olefin oxide; With tolylene diamine and tri-isopropanolamine as compound initiator by with resulting polyethers 15～30 weight parts of the addition reaction of olefin oxide; With glycerine as initiator by with resulting polyethers 5～20 weight parts of the addition reaction of olefin oxide, 100 parts of the compound polyethers of being formed;
(b) contain composite catalyst 1.6～3.3 weight parts of kicker, gel catalyst and catalyst for trimerization;
(c) whipping agent 7～16 weight parts;
(d) water 1.5～3.0 weight parts;
(e) suds-stabilizing agent 1.4～4.0 weight parts;
(f) polymeric isocyanate is a benchmark with above-mentioned compound polyethers and water, and its index is 95～150.
The olefin oxide that the present invention is used for synthesizing polyether is meant the mixture of ethylene oxide (EO) and propylene oxide (PO), and their weight ratio is PO: EO=100～30: 0～30.
Kicker of the present invention is the mixture of one or more arbitrary proportions in pentamethyl-diethylenetriamine, two-dimethyl amine benzyl ethyl ether or the 4-methyl hexamethylene diamine; Described gel catalyst is the mixture of one or more arbitrary proportions in dimethylcyclohexylamine, triethylene diamine, the dimethyl benzylamine; Described catalyst for trimerization is the mixture of one or more arbitrary proportions in first quaternary amine, second quaternary amine, hot quaternary amine, the hexahydrotriazine, as TMR-2, TMR-3, the C41 of U.S.'s gas companies.
Whipping agent among the present invention is meant the mixture of pentamethylene, iso-pentane or their any part by weight.
Suds-stabilizing agent among the present invention is a kind of tensio-active agent, and it is meant the silicon class tensio-active agent that contains the Si-C structure.Comprise German Sa company and hard bubble and use the suds-stabilizing agent silicide, as B8460, B8461, B8462, B846588471, B8474, B8476, B8481 etc.; The silicide of GE company has the foam stabilizer DC5604 of L6900, L6988, L6912 and gas companies, and dolantin generation wound company produces suds-stabilizing agent AK8805, AK8815, AK8812, AK8809 etc.The main effect of suds-stabilizing agent has the size that reduces surface tension, improves Combination, the even bubble that produces and regulates the foamy structure,
Polymeric isocyanate among the present invention is meant the polymethine polyphenyl polyisocyanate, is benchmark with above-mentioned compound polyethers and water, and its index is 95～150.The common NCO percentage composition of polymeric isocyanate is 30.5～31.5%.The polymeric isocyanate index is meant the weight ratio of actual add-on of isocyanic ester and Theoretical Calculation amount, Theoretical Calculation amount=(NCO percentage composition * 1000)+(0.749 * 6234) * water add-on/(NCO percentage composition * 1000), (the average hydroxyl value of 0.749 * compound polyethers) * 100/.
Adoptable polymeric isocyanate comprises 44V-20L, 44V-10L, the 44V-40L of Bayer company, the Suprasec5005 of Huntsman company, Suprasec2085, Suprasec5000, the M20S of BASF AG, the PAPI27 of DOW company, PAPI135, Mitsui MR200, MR100, the Yantai Wan Hua PM2010 of company, PM200 etc.
The present invention can also contain organic fire-retardant, its consumption in prescription is 0～30 weight part, it specifically is the mixture of one or more arbitrary proportions among tricresyl phosphate (1-chloro-second propyl group) ester TCPP, three (1,3-two chloropropyls) phosphoric acid ester TDCP, three (β-chloroethyl) phosphoric acid ester TCEP or the dimethyl methyl phosphonate DMMP.
The present invention also can contain following optional be 0～10 weight part auxiliary material and/or additive and/or filler; Described auxiliary material is selected from a-vinyl toluene, dimethyl polysiloxane or paraffin wax or Fatty Alcohol(C12-C14 and C12-C18); Described additive is selected from tinting material, antiaging agent, softening agent or has mildew-resistant and the material of fungistatic effect; Described filler is selected from whitening agent, tripoli; Aforementioned auxiliary material, additive, filler can use separately, also can two or morely be used with arbitrary proportion.
Organic fire-retardant or auxiliary material and/or additive can add simultaneously or add separately.
In general, hard polyurethane foams is that (40 ℃-55 ℃) were made through certain set time at a certain temperature after reaction solution was injected the foaming aluminum dipping form.But because the length of its time produces the phenomenon of rate of expansion difference can cause from the anchor clamps depanning time.Rate of expansion after this polyurethane foam foaming will be directly connected to the size and the deflection of refrigerator product.Basically be that it is directly proportional with size, thickness, and produce the phenomenon that foaming after rate increases.To same mould, when reaction mass increases, owing to the restriction that is subjected to mould, the foamy compact density increases, and easily causes rate of expansion to increase like this after the demoulding.Hence one can see that, and foam density is high more, and rate of expansion is low more, and demolding performace is just good more.
By a large amount of practices, can adopt following method to assess the foamy demolding performace:
To measure hard polyurethane foam component in advance fully stirs, mix, pour into to be of a size of in 400 * 400 * 80 the aluminum dipping form and carry out airtight foaming, the demoulding in the time of 3 minutes, measure the thickness in foam centre and the thickness difference of edge in the time of 6 minutes, and calculate the foam expansion rate.Measure foamy sandwich layer density after 1 day.By aforesaid method, the foam of assessing out the preparation of different constituents when the demoulding in 3 minutes, under certain density, the rate of expansion of measuring in 6 minutes.
The present invention compared with prior art has tangible advantage.
Have when 1, the present invention foams good flowing property and fast demolding performace are arranged, demould time can reach 3 minutes, and the demould time of prior art is 6 minutes;
2, the present invention adopts that the whipping agent of zero odp---pentane foams, and is environmentally friendly;
3, the hard polyurethane foams of employing the present invention preparation has favorable mechanical performance and better dimensional stability compared with prior art
Embodiment
Describe the present invention in more detail below by (being applied to the refrigerator field is example) embodiment and comparative example, but the present invention is not limited in these examples.
(1) polyethers A hydroxyl value is the sucrose propylene oxide polyethers of 320～450mgKOH/g;
(2) polyethers B hydroxyl value is the sorbyl alcohol propylene oxide polyethers of 440～560mgKOH/g;
(3) polyethers C hydroxyl value is tolylene diamine and the tri-isopropanolamine propylene oxide oxyethane polyethers of 400～460mgKOH/g;
(4) polyethers D hydroxyl value is the glycerine propylene oxide polyethers of 440～560mgKOH/g;
(5) polyethers E hydroxyl value is the sucrose propylene glycol propylene oxide polyethers of 400～460mgKOH/g;
(6) polyethers F hydroxyl value is the glycerine propylene oxide polyethers of 170～280mgKOH/g;
(7) polyethers G hydroxyl value is the sucrose glycerine propylene oxide polyethers of 480～530mgKOH/g.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Polyethers A | 50 | 42 | 60 | 30 | 30 |
| Polyethers B | 15 | 20 | 5 | / | / |
| Polyethers C | 20 | 30 | 20 | 15 | 15 |
| Polyethers D | 15 | / | 15 | / | / |
| Polyethers E | / | / | / | 40 | 30 |
| Polyethers F | / | 8 | / | / | |
| Polyethers G | / | / | / | 10 | 20 |
| Composite catalyst | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| Water | 2.0 | 2.0 | 2.1 | 2.0 | 2.0 |
| Pentamethylene | 12 | 9 | / | 12 | 12 |
| Iso-pentane | / | 4 | 9 | / | / |
| B8462 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| The 44V20L index | 110 | 110 | 110 | 110 | 110 |
| Flow index | 0.735 | 0.742 | 0.748 | 0.744 | 0.740 |
| Demould time, minute | 3 | 3 | 3 | 3 | 6 |
| Foamed core density kg/m 3 | 40.2 | 41.0 | 40.7 | 37.8 | 40.0 |
| Foam expansion, mm | 2.1 | 1.8 | 2.3 | Cracking | 2.0 |
| Foam thermal conductivity (mW/m.K) | 20.2 | 21.6 | 22.0 | / | 20.3 |
| Foam compression intensity (MPa) | 0.206 | 0.198 | 0.212 | / | 0.193 |
| Rate of expansion (%) | 2.63 | 2.25 | 2.88 | / | 2.50 |
| Low temperature size changing rate (%) | 0.12 | 0.08 | 0.07 | / | 0.15 |
| High temperature size changing rate (%) | 0.10 | 0.16 | 0.20 | / | 0.36 |
Continuous table
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | |
| Polyethers A | 55 | 30 | 50 | 30 |
| Polyethers B | 20 | 25 | 15 | / |
| Polyethers C | 20 | 25 | 25 | 15 |
| Polyethers D | 5 | 15 | 10 | / |
| Polyethers E | / | / | / | 30 |
| Polyethers F | / | 5 | / | / |
| Polyethers G | / | / | / | 20 |
| Composite catalyst | 3.0 | 3.0 | 3.0 | 3.0 |
| Water | 2.0 | 2.0 | 2.0 | 2.0 |
| Pentamethylene | 10 | 8 | 7 | 10 |
| Iso-pentane | 3 | 5 | 7 | 3 |
| B8462 | 2.5 | 2.5 | 2.5 | 2.5 |
| The 44V20L index | 110 | 110 | 110 | 110 |
| Demould time, minute | 3 | 3 | 3 | 6 |
| Flow index | 0.748 | 0.760 | 0.753 | 0.740 |
| Foamed core density kg/m 3 | 41.6 | 41.3 | 41.2 | 40.8 |
| Foam expansion, mm | 2.7 | 2.8 | 2.5 | 2.4 |
| Foam thermal conductivity (mW/m.K) | 21.2 | 21.5 | 21.6 | 21.8 |
| Foam compression intensity (MPa) | 0.210 | 0.204 | 0.195 | 0.197 |
| Rate of expansion (%) | 3.4 | 3.5 | 3.1 | 3.0 |
| Low temperature size changing rate (%) | 0.20 | 0.14 | 0.16 | 0.17 |
| High temperature size changing rate (%) | 0.15 | 0.30 | 0.22 | 0.32 |
Annotate: go up in the table
I) raw material is all with listed as parts by weight;
Ii) foamy density, pressure intensity, high low temperature size changing rate, thermal conductivity are all measured by national standard.
Ii) foamy sandwich layer density is meant the density except that the exterior skin part in the foam that foams in identical anchor clamps, utilizes electronic scales and dimension measuring device to measure.
Iv) flow index is meant at the tubular foam-in-mould of fixed, the foamy height of making and the ratio of weight.
The above, it only is inventive embodiments, be not that the present invention is done any pro forma restriction, any personnel that are familiar with this technology may utilize the technology contents of above-mentioned announcement to be changed or be modified to the equivalent embodiment of equivalent variations, every content that does not break away from technical solution of the present invention all still belongs in the scope of technical solution of the present invention.
Claims (11)
1, a kind of hard polyurethane foam component with fast demolding performace is characterized in that comprising following moiety:
(a) by with sucrose as initiator by with resulting polyethers 30～60 weight parts of the addition reaction of olefin oxide, with sorbic alcohol as initiator by with resulting polyethers 5～25 weight parts of the addition reaction of olefin oxide, with tolylene diamine and tri-isopropanolamine as compound initiator by with resulting polyethers 15～30 weight parts of the addition reaction of olefin oxide, with glycerine as initiator by 100 parts of the compound polyethers formed with resulting polyethers 5～20 weight parts of the addition reaction of olefin oxide;
(b) composite catalyst 1.6～3.3 weight parts of forming by kicker, gel catalyst and catalyst for trimerization;
(c) whipping agent 7～16 weight parts;
(d) water 1.5～3.0 weight parts;
(e) suds-stabilizing agent 1.4～4.0 weight parts;
(f) polymeric isocyanate is a benchmark with above-mentioned compound polyethers and water, and its index is 95～150.
2, the hard polyurethane foam component with fast demolding performace according to claim 1, it is characterized in that wherein can also containing the organic fire-retardant of 0～30 weight part, described organic fire-retardant is the mixture of one or more arbitrary proportions among tricresyl phosphate (1 chloro-second propyl group) ester TCPP, three (1,3-two chloropropyls) phosphoric acid ester TDCP, three (β-chloroethyl) phosphoric acid ester TCEP or the dimethyl methyl phosphonate DMMP.
3, the hard polyurethane foam component with fast demolding performace according to claim 1 is characterized in that wherein also can containing auxiliary material and/or the additive and/or the filler of 0～10 weight part; Described auxiliary material is selected from alpha-methyl styrene, dimethyl polysiloxane or paraffin wax or Fatty Alcohol(C12-C14 and C12-C18); Described additive is selected from tinting material, antiaging agent, softening agent or has mildew-resistant and the material of fungistatic effect; Described filler is selected from whitening agent, tripoli; Aforementioned auxiliary material, additive, filler can use separately, also can two or morely be used with arbitrary proportion.
4, according to claim 1 or 2 or 3 described hard polyurethane foam components, it is characterized in that described olefin oxide is meant that ethylene oxide and propylene oxide are by 100～30: the mixture that 0～30 weight ratio is formed with fast demolding performace.
5,, it is characterized in that described kicker is the mixture of one or more arbitrary proportions in pentamethyl-diethylenetriamine, two-dimethyl amine benzyl ethyl ether or the 4-methyl hexamethylene diamine according to claim 1 or 2 or 3 described hard polyurethane foam components with fast demolding performace; Described gel catalyst is the mixture of one or more arbitrary proportions in dimethylcyclohexylamine, triethylene diamine, the dimethyl benzylamine; Described catalyst for trimerization is the mixture of one or more arbitrary proportions in first quaternary amine, second quaternary amine, hot quaternary amine, the hexahydrotriazine.
6,, it is characterized in that wherein said whipping agent is meant the mixture of pentamethylene, iso-pentane or their any part by weight according to claim 1 or 2 or 3 described hard polyurethane foam components with fast demolding performace.
7,, it is characterized in that described suds-stabilizing agent is meant the silicon class tensio-active agent that contains the Si-C structure according to claim 1 or 2 or 3 described hard polyurethane foam components with fast demolding performace.
8, according to claim 1 or 2 or 3 described hard polyurethane foam components, it is characterized in that described polymeric isocyanate is meant the polymethine polyphenyl polyisocyanate with fast demolding performace.
9,, it is characterized in that be 300～600mgKOH/g as initiator by the hydroxyl value with the resulting polyethers of addition reaction of olefin oxide with sucrose according to claim 1 or 2 or 3 described hard polyurethane foam components with fast demolding performace; Is 350～650mgKOH/g as initiator by the hydroxyl value with the resulting polyethers of addition reaction of olefin oxide with sorbic alcohol; Is 350～700mgKOH/g as compound initiator by the hydroxyl value with the resulting polyethers of addition reaction of olefin oxide with tolylene diamine and tri-isopropanolamine; Is 160～580mgKOH/g as initiator by the hydroxyl value with the resulting polyethers of addition reaction of olefin oxide with glycerine.
10, according to claim 1 or 2 or 3 described rigid polyurethane foam combinations with fast demolding performace, it is characterized in that 3 minutes just can the completely solidified moulding.
11, the rigid polyurethane foam combination with fast demolding performace according to claim 10, it is characterized in that 3 minutes can the completely solidified moulding be to mix just by composition, pour foaming inclosed molds in 400 * 400 * 80 the mould into, the demoulding after 3 minutes, measure foamy core density 〉=40kg/m after measuring its rate of expansion≤3.5%, 1 day after 6 minutes
3Simulate assessment.
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| CN200610041382A CN1986593B (en) | 2006-08-18 | 2006-08-18 | Hard polyurethane foam composition with fast demolding performace |
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| CN1986593B CN1986593B (en) | 2010-05-12 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199373A (en) * | 2015-10-09 | 2015-12-30 | 蚌埠市天源气体有限责任公司 | Compression-resistant thermal-insulation material for low-temperature pipelines and preparation method thereof |
| CN108840985A (en) * | 2018-05-22 | 2018-11-20 | 南京红宝丽聚氨酯有限公司 | A kind of rigid polyurethane foam and preparation method thereof for refrigerator |
| CN109642004A (en) * | 2016-05-20 | 2019-04-16 | 科思创德国股份有限公司 | Polyurethane foam and compound polyurethane material comprising it |
| CN110028645A (en) * | 2019-03-19 | 2019-07-19 | 广州朗腾聚氨酯有限公司 | A kind of fast demoulding combined polyether and its polyurethane and preparation method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3927244A1 (en) * | 1989-08-18 | 1991-02-21 | Basf Ag | TRANSPARENT, COMPRESSABLE, STEAM-STEAMABLE, COMPACT POLYURETHANE POWDERING, PROCESS FOR THEIR PRODUCTION AND THEIR USE, IN PARTICULAR FOR MEDICAL TECHNICAL ITEMS |
| WO2000004070A1 (en) * | 1998-07-15 | 2000-01-27 | Huntsman Ici Chemicals Llc | Process for rigid polyurethane foams |
| DE102004017294A1 (en) * | 2004-04-05 | 2005-10-20 | Basf Ag | Process for the production of polyurethane foams |
-
2006
- 2006-08-18 CN CN200610041382A patent/CN1986593B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199373A (en) * | 2015-10-09 | 2015-12-30 | 蚌埠市天源气体有限责任公司 | Compression-resistant thermal-insulation material for low-temperature pipelines and preparation method thereof |
| CN109642004A (en) * | 2016-05-20 | 2019-04-16 | 科思创德国股份有限公司 | Polyurethane foam and compound polyurethane material comprising it |
| CN109642004B (en) * | 2016-05-20 | 2021-08-17 | 科思创德国股份有限公司 | Polyurethane foam and polyurethane composite material containing same |
| CN108840985A (en) * | 2018-05-22 | 2018-11-20 | 南京红宝丽聚氨酯有限公司 | A kind of rigid polyurethane foam and preparation method thereof for refrigerator |
| CN110028645A (en) * | 2019-03-19 | 2019-07-19 | 广州朗腾聚氨酯有限公司 | A kind of fast demoulding combined polyether and its polyurethane and preparation method |
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| CN1986593B (en) | 2010-05-12 |
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Assignee: Nanjing Baoxin Polyurethane Co., Ltd. Assignor: Hongbaoli Co., Ltd., Nanjing Contract record no.: 2012320000039 Denomination of invention: Hard polyurethane foam composition with fast demolding performace Granted publication date: 20100512 License type: Exclusive License Open date: 20070627 Record date: 20120117 |
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Granted publication date: 20100512 Termination date: 20200818 |