CN102936329A - Polyurethane composite material for refrigeratory spray coating and preparation method thereof - Google Patents
Polyurethane composite material for refrigeratory spray coating and preparation method thereof Download PDFInfo
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- CN102936329A CN102936329A CN2012104786122A CN201210478612A CN102936329A CN 102936329 A CN102936329 A CN 102936329A CN 2012104786122 A CN2012104786122 A CN 2012104786122A CN 201210478612 A CN201210478612 A CN 201210478612A CN 102936329 A CN102936329 A CN 102936329A
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Abstract
The invention relates to a polyurethane composite material for refrigeratory spray coating and a preparation method thereof. The composite material is composed of a component A and a component B in a weight ratio of 1:(1-1.05), wherein the component A is composed of polyether glycol, polyester polyol, crosslinking agent, foam stabilizer, foaming agent, catalyst, flame retardant and other assistants; and the component B is polymethylene polyphenyl polyisocyanate. The preparation method comprises the following steps: sequentially adding the components in the component A into a reaction kettle, and thoroughly mixing for 0.5-1.5 hours at normal temperature; and evenly mixing the component A and the component B in a weight ratio of 1:(1-1.05) with a high-pressure spray coater, atomizing, foaming, and quickly forming and aging the foam to obtain the product. The foam provided by the invention has the advantages of low heat conductivity coefficient, excellent low-temperature dimensional stability, high strength, excellent flame retardancy (the fireproofing grade reaches Grade B1), favorable binding property with the substrate, uniform density distribution and smooth surface, and is especially suitable for refrigeratory spray coating construction.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of polyurethane combined material for freezer and preparation method thereof.
Background technology
The freezer heat insulating work is mainly taked composite laminboard assembling and the spraying dual mode that hard bubbles at present.The sandwich board assembling mode has the advantages such as convenient and swift, but uses this kind mode will face inconvenience in the various irregular miniature cold storage construction process of structure.The in-situ spraying method of hard bubbling does not produce the assembly unit space owing to existing and can construct flexibly, and insulation effect is excellent, and the cohesive strength high more and more is applied to the freezer heat insulating work.
But the combined polyether for preparing at present the use of hard polyurethane foam spray material adopts 141b(one fluorine ethylene dichloride more) as pneumatogen, the one, not environmental protection, the polyurethane foam stability that the two makes is bad, and thermal conductivity is high, is unfavorable for energy-saving consumption-reducing.
HFC-365mfc(1,1,1,3,3-3-pentafluorobutane) belong to third generation blowing agents, 40.2 ℃ of boiling points be the unique liquid whipping agent that is higher than room temperature of HFC whipping agent product mid-boiling point of all zero odps, but shortcoming are to have certain combustibility; HFC-134a(1,1,1,2-Tetrafluoroethane), ODP=0, nontoxic, tasteless, colourless, do not fire, not quick-fried, Heat stability is good, to urethane foam without plasticization effect, but it is lower that its shortcoming is boiling point, is gas under the room temperature, therefore will be transformed original foaming machine when using separately.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of polyurethane combined material for freezer, polyurethane rigid foam material environmental protection, the heat insulating ability that it makes is good, good stability of the dimension; Simultaneously the present invention also provides the method for preparing this combination material.
Technical scheme of the present invention is: the polyurethane combined material that is used for freezer, be comprised of component A and B component, the weight ratio of component A and B component is 1:1～1.05, wherein, described component A is composed of the following components: polyether glycol, 20～35, polyester polyol, 6～20, linking agent, 6～11, suds-stabilizing agent, 1～1.5, whipping agent, 8～25, catalyzer, 2.5～4.5, fire retardant, 10～25, other auxiliary agents, 1.5～5.0; Above each numerical value is each component shared weight percentage in component A; Described B component is the polymethine polyphenyl polyisocyanate.
The preparation method of aforesaid combination material may further comprise the steps:
A, preparation raw material: prepare raw material by following component:
Component A: described component A is composed of the following components: polyether glycol, 20～35, polyester polyol, 6～20, linking agent, 6～11, suds-stabilizing agent, 1～1.5, whipping agent, 8～25, catalyzer, 2.5～4.5, fire retardant, 10～25, other auxiliary agents, 1.5～5.0; Above each numerical value is each component shared weight percentage in component A;
B component: polymethine polyphenyl polyisocyanate;
The weight ratio of component A and B component is 1:1～1.05;
B, preparation component A: according to component and weight ratio among the step a, to stir in load weighted polyether glycol and the polyester polyol adding reactor, add linking agent, suds-stabilizing agent, whipping agent, catalyzer, fire retardant and other auxiliary agents, stirred at normal temperatures 0.5～1.5 hour, fully mix;
C, according to component and weight ratio among the step a, the B component weighing is for subsequent use;
When d, use, component A is evenly mixed by high-pressure spraying machine by the weight ratio of A:B=1:1～1.05 with B component, the atomizing foaming, the rapid moulding slaking of foam makes product.
Among the component A described above: described polyether glycol is 3～8 functionality, number-average molecular weight is 1500～5000 combined polyether glycol, and it comprises: sucrose polyethers, 35～50, amidogen ether, 14～20, Amino Terminated polyether(ATPE), 14～15 mixes initiator polyethers, 15～36; Above each numerical value is each component shared weight percentage in component A; Described polyester polyol is viscosity 2000～3000mpa.s/25 ℃, acid number 0.2～0.8mgKOH/g low acid number polyester polyol; Described pneumatogen is the mixture of 1,1,1,3,3-3-pentafluorobutane and HFA 134a, and both weight ratios are: 1,1,1,3,3-3-pentafluorobutane: the mixture=93:7 of HFA 134a.
When HFC-365/134a mixed with 93:7, mixture was liquid under the room temperature without flash-point, is non-flammable mixed foaming agent, and thermal conductivity (25 ℃) is 10.9, therefore belong to floride-free type combined polyether with its combined polyether of producing, has the characteristics of environmental protection.Adopt the freezer polyurethane rigid foam material of HFC-365mfc/134a type whipping agent, when reaching the environmental protection effect, all reach advanced world standards at aspects such as specific tenacity, cohesiveness, low temperature dimensional stability, flame retardant resistances.
Described linking agent is number-average molecular weight at 100～200 pure Ammonia material, preferred TEA(trolamine) or the TIPA(tri-isopropanolamine) etc.
Described suds-stabilizing agent is non-hydrolysis silicon-carbon class tensio-active agent, and preferred B8538(wins the wound Degussa)
Described catalyzer is one or more in the low smell catalyzer of tertiary amines or the low smell catalyzer of triazines or the tin class catalyzer, preferred triethylene diamine, pentamethyl-diethylenetriamine, 1, in 3,5-three (dimethylamino-propyl)-hexahydrotriazine or the dibutyl tin laurate one or more.
Described fire retardant is TCPP(three (2-chloropropyl) phosphoric acid ester), the DMMP(dimethyl methyl phosphonate), the APP(ammonium polyphosphate) or trimeric cyanamide in one or more.
Described other auxiliary agents are one or more in mill base, antioxidant, pigment or the solubilizing agent.
Beneficial effect of the present invention is:
1, various raw material consistencies are good in the system, can prolong the storage time of combination material.
2, can operate at normal temperatures and pressures in preparation process and the construction process.
3, the polyurethane coating foam materials environmental protection that makes, thermal conductivity is low, and the low temperature dimensional stability is splendid, and intensity is high, and cohesiveness is good between the base material, and density distribution is even, and surfacing is particularly suitable for the freezer construction.
4, the polyurethane coating foam materials flame retardant properties that makes is splendid, and fire rating reaches the B1 level, and foaming properties can reach the standard-required of GB GB/T 10294-2008, JC/T 998-2006 fully.
Embodiment
Specify the present invention below in conjunction with embodiment.
Embodiment 1:
1, preparation component A, 100kg: difference weighing sucrose polyethers, 10kg, amidogen ether, 4kg mix initiator polyethers, 3kg, Amino Terminated polyether(ATPE), 3kg, low acid number polyester, 20kg; Suds-stabilizing agent B-8538(wins the wound Degussa), 1.0kg, whipping agent 1,1,1,3,3-3-pentafluorobutane/1,1,1,2-Tetrafluoroethane (1,1,1,3,3-3-pentafluorobutane and 1,1,1, the mixture of 2-Tetrafluoroethane, both weight ratios are: 1,1,1,3,3-3-pentafluorobutane: 1, the mixture of 1,1,2-Tetrafluoroethane=93:7), 25kg, linking agent TEA, 6kg, catalyzer is selected pentamethyl-diethylenetriamine, triethylene diamine, the mixture of 1,3,5-three (dimethylamino-propyl)-hexahydrotriazine and dibutyl tin laurate, weight is respectively 1.0kg, 1.5kg, 0.7kg and 0.2kg, fire retardant TCPP, 20kg, other selection of auxiliary oxidation inhibitor and solubilizing agent, weight is respectively 2kg and 2.6kg.
Load weighted above-mentioned raw materials is added in the reactor, stirred at normal temperatures 0.5 hour, fully mix.
2, B component polymethine polyphenyl polyisocyanate, 100kg.
3, component A is evenly mixed by high-pressure spraying machine according to weight ratio 1:1 with B component, the atomizing foaming, density 28.6kg/m is wherein freely steeped in the rapid moulding slaking of foam
3, expansion rate is controlled at cream time 3-4 second, gel time 8-10 second makes polyurethane rigid foam material, and the product quality indicator that makes sees Table 1.
Embodiment 2:
1, preparation component A, 100kg: difference weighing sucrose polyethers, 15kg, amidogen ether, 5kg mix initiator polyethers, 10kg, Amino Terminated polyether(ATPE), 5kg, low acid number polyester, 12kg; Suds-stabilizing agent B-8538(wins the wound Degussa), 1.5kg, whipping agent 1,1,1,3,3-3-pentafluorobutane/1,1,1,2-Tetrafluoroethane (1,1,1,3,3-3-pentafluorobutane and 1,1,1, the mixture of 2-Tetrafluoroethane, both weight ratios are: 1,1,1,3,3-3-pentafluorobutane: 1, the mixture of 1,1,2-Tetrafluoroethane=93:7), 8kg, linking agent TEA, 11kg, catalyzer is selected pentamethyl-diethylenetriamine, triethylene diamine, 1,3, the mixture of 5-three (dimethylamino-propyl)-hexahydrotriazine and dibutyl tin laurate, weight is respectively 1.0kg, 1.8kg, 0.6kg and 0.2kg, fire retardant is selected the mixture of TCPP and DMMP, weight is respectively 20kg and 5kg, other selection of auxiliary solubilizing agent and mill bases, weight is respectively 2.7kg and 1.2kg.
Load weighted above-mentioned raw materials is added in the reactor, stirred at normal temperatures 0.5 hour, fully mix.
2, B component polymethine polyphenyl polyisocyanate, 100kg.
3, component A is evenly mixed by high-pressure spraying machine according to weight ratio 1:1 with B component, the atomizing foaming, density 28.8kg/m is wherein freely steeped in the rapid moulding slaking of foam
3, expansion rate is controlled at cream time 3-4 second, gel time 8-10 second makes polyurethane rigid foam material, and the product quality indicator that makes sees Table 1.
Embodiment 3:
1, preparation component A, 100kg: difference weighing sucrose polyethers, 12kg, amidogen ether 403,5kg mix initiator polyethers, 12kg, Amino Terminated polyether(ATPE), 5kg, low acid number polyester, 8kg; Suds-stabilizing agent B-8538(wins the wound Degussa), 1.5kg, whipping agent 1,1,1,3,3-3-pentafluorobutane/1,1,1,2-Tetrafluoroethane (1,1,1,3,3-3-pentafluorobutane and 1,1,1, the mixture of 2-Tetrafluoroethane, both weight ratios are: 1,1,1,3,3-3-pentafluorobutane: 1, the mixture of 1,1,2-Tetrafluoroethane=93:7), 24kg, linking agent TEA, 11kg, catalyzer is selected pentamethyl-diethylenetriamine, triethylene diamine, the mixture of 1,3,5-three (dimethylamino-propyl)-hexahydrotriazine and dibutyl tin laurate, weight is respectively 1.3kg, 1.8kg, 1kg and 0.4kg, fire retardant TCPP, 12kg, other selection of auxiliary oxidation inhibitor and solubilizing agent, weight is respectively 3.5kg and 1.5kg.
Load weighted above-mentioned raw materials is added in the reactor, stirred at normal temperatures 1 hour, fully mix.
2, B component polymethine polyphenyl polyisocyanate, 105kg.
3, component A is evenly mixed by high-pressure spraying machine according to weight ratio 1:1.05 with B component, the atomizing foaming, density 29.0kg/m is wherein freely steeped in the rapid moulding slaking of foam
3, expansion rate is controlled at cream time 3-4 second, gel time 8-10 second makes polyurethane rigid foam material, and the product quality indicator that makes sees Table 1.
Table 1 is the froth product quality examination data of embodiment 1～3.
The froth product quality examination data of table 1: embodiment 1～3
As seen from the above table: without destruction, environmental-protecting performance is excellent to ozonosphere for the combined polyether product; The polyurethane foam thermal conductivity that makes is low, good leak tightness, and flame retardant properties is excellent, product stability good.
Claims (10)
1. a polyurethane combined material that is used for freezer is characterized in that, be comprised of component A and B component, the weight ratio of component A and B component is 1:1～1.05, wherein,
Described component A is composed of the following components: polyether glycol, 20～35, polyester polyol, 6～20, linking agent, 6～11, suds-stabilizing agent, 1～1.5, whipping agent, 8～25, catalyzer, 2.5～4.5, fire retardant, 10～25, other auxiliary agents, 1.5～5.0; Above each numerical value is each component shared weight percentage in component A;
Wherein among the component A: described polyether glycol is 3～8 functionality, and number-average molecular weight is 1500～5000 combined polyether glycol, comprises sucrose polyethers, amidogen ether, Amino Terminated polyether(ATPE) and mixing initiator polyethers; Described polyester polyol is viscosity 2000～3000mpa.s/25 ℃ low acid number polyester polyol; Described pneumatogen is the mixture of 1,1,1,3,3-3-pentafluorobutane and HFA 134a, and both weight ratios are: 1,1,1,3,3-3-pentafluorobutane: the mixture=93:7 of HFA 134a;
Described B component is the polymethine polyphenyl polyisocyanate.
2. the polyurethane combined material for freezer according to claim 1 is characterized in that, described linking agent is number-average molecular weight at 100～200 pure Ammonia material.
3. the polyurethane combined material for freezer according to claim 1 is characterized in that, described suds-stabilizing agent is non-hydrolysis silicon-carbon class tensio-active agent.
4. the polyurethane combined material for freezer according to claim 1, it is characterized in that, described catalyzer is triethylene diamine, N, N, N '; N ", N "-five methyl diethylentriamine, 1; one or more in 3,5-three (dimethylamino-propyl)-hexahydrotriazine or the dibutyl tin laurate.
5. the polyurethane combined material for freezer according to claim 1 is characterized in that, described fire retardant is one or more in three (2-chloropropyl) phosphoric acid ester, dimethyl methyl phosphonate, ammonium polyphosphate or the trimeric cyanamide.
6. be used for the preparation method of the polyurethane combined material of freezer, it is characterized in that, may further comprise the steps:
A, preparation raw material: prepare raw material by following component:
Component A: polyether glycol, 20～35, polyester polyol, 6～20, linking agent, 6～11, suds-stabilizing agent, 1～1.5, whipping agent, 8～25, catalyzer, 2.5～4.5, fire retardant, 10～25, other auxiliary agents, 1.5～5.0; Above each numerical value is each component shared weight percentage in component A;
Wherein: described polyether glycol is 3～8 functionality, and number-average molecular weight is 1500～5000 combined polyether glycol, comprises sucrose polyethers, amidogen ether, Amino Terminated polyether(ATPE) and mixing initiator polyethers; Described polyester polyol is viscosity 2000～3000mpa.s/25 ℃ of low acid number polyester polyol; Described pneumatogen is the mixture of 1,1,1,3,3-3-pentafluorobutane and HFA 134a, and both weight ratios are: 1,1,1,3,3-3-pentafluorobutane: the mixture=93:7 of HFA 134a;
B component: polymethine polyphenyl polyisocyanate;
The weight ratio of component A and B component is 1:1～1.05;
B, preparation component A: according to component and weight ratio among the step a, to stir in load weighted polyether glycol and the polyester polyol adding reactor, add linking agent, suds-stabilizing agent, whipping agent, catalyzer, fire retardant and other auxiliary agents, stirred at normal temperatures 0.5～1.5 hour, fully mix;
C, according to component and weight ratio among the step a, the B component weighing is for subsequent use;
D, when using, component A mixed getting final product with B component.
7. the preparation method of combination material according to claim 6 is characterized in that, described linking agent is number-average molecular weight at 100～200 pure Ammonia material.
8. the preparation method of combination material according to claim 6 is characterized in that, described suds-stabilizing agent is non-hydrolysis silicon-carbon class tensio-active agent.
9. the preparation method of combination material according to claim 6 is characterized in that, described catalyzer is triethylene diamine, N, N, N ', N ", N "-five methyl diethylentriamine, in 1,3,5-three (dimethylamino-propyl)-hexahydrotriazine or the dibutyl tin laurate one or more.
10. the preparation method of combination material according to claim 6 is characterized in that, described fire retardant is one or more in three (2-chloropropyl) phosphoric acid ester, dimethyl methyl phosphonate, ammonium polyphosphate or the trimeric cyanamide.
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| CN103254880A (en) * | 2013-03-07 | 2013-08-21 | 河南煤业化工集团研究院有限责任公司 | Gas-extraction hole-sealing material |
| CN104892892A (en) * | 2015-06-11 | 2015-09-09 | 山东一诺威新材料有限公司 | Polyurethane composite material for spray coating for underground garage |
| CN105294989A (en) * | 2015-10-14 | 2016-02-03 | 江苏绿源新材料有限公司 | Biology base polyurethane spray coating foam plastic and preparation method of biology base polyurethane spray coating foam plastic |
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| CN103254880A (en) * | 2013-03-07 | 2013-08-21 | 河南煤业化工集团研究院有限责任公司 | Gas-extraction hole-sealing material |
| CN104892892A (en) * | 2015-06-11 | 2015-09-09 | 山东一诺威新材料有限公司 | Polyurethane composite material for spray coating for underground garage |
| CN105294989B (en) * | 2015-10-14 | 2017-12-22 | 江苏绿源新材料有限公司 | Bio-based polyurethane sprayed-on plastic foam and preparation method thereof |
| CN105294989A (en) * | 2015-10-14 | 2016-02-03 | 江苏绿源新材料有限公司 | Biology base polyurethane spray coating foam plastic and preparation method of biology base polyurethane spray coating foam plastic |
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| CN106085099A (en) * | 2016-07-29 | 2016-11-09 | 神盾防火科技有限公司 | A kind of heat preservation of refrigeration storage composition of insulating mold coating and preparation method thereof |
| CN107793908A (en) * | 2016-09-01 | 2018-03-13 | 纳米及先进材料研发院有限公司 | Coating composition and the method that the characteristics such as self-healing are assigned to substrate |
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| CN107298748B (en) * | 2017-06-19 | 2020-05-22 | 山西省建筑科学研究院有限公司 | Environment-friendly degradable flame-retardant polyurethane rapid packaging material and preparation method thereof |
| CN108641115A (en) * | 2018-05-14 | 2018-10-12 | 苏州健能新材料科技有限公司 | The preparation method of dual-component polyurethane foaming agent |
| CN109457879A (en) * | 2018-12-27 | 2019-03-12 | 广州市明煌保温节能材料有限公司 | A kind of roofing waterproof heat insulation integrated material and its spray paint and its manufacturing process |
| CN110128622A (en) * | 2019-05-14 | 2019-08-16 | 包头北方创业有限责任公司 | Bitumen transportation device and its production method |
| CN113045980A (en) * | 2019-12-27 | 2021-06-29 | 洛阳科博思新材料科技有限公司 | Surface protective coating, preparation method thereof and synthetic sleeper |
| CN111320737A (en) * | 2020-04-13 | 2020-06-23 | 南京红宝丽聚氨酯有限公司 | Polyurethane raw material composition, preparation method and application of polyurethane rigid foam |
| CN111320737B (en) * | 2020-04-13 | 2022-04-15 | 南京红宝丽聚氨酯有限公司 | Polyurethane raw material composition, preparation method and application of polyurethane rigid foam |
| CN112661932A (en) * | 2020-12-23 | 2021-04-16 | 上海玓墨化工科技有限公司 | Spraying type environment-friendly rigid polyurethane foam raw material composition for pipeline |
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Application publication date: 20130220 |