CN101550241B - Environment protection type high-efficiency multiple mixing aerating powder for PU rigid foam - Google Patents
Environment protection type high-efficiency multiple mixing aerating powder for PU rigid foam Download PDFInfo
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- CN101550241B CN101550241B CN2009101168189A CN200910116818A CN101550241B CN 101550241 B CN101550241 B CN 101550241B CN 2009101168189 A CN2009101168189 A CN 2009101168189A CN 200910116818 A CN200910116818 A CN 200910116818A CN 101550241 B CN101550241 B CN 101550241B
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Abstract
An environment protection type high-efficiency multiple mixing aerating powder for a PU rigid foam is composed of by weight 5-15 shares of HC, 2-20 shares of HFC, and 0-10 shares of adjuvant species; HC is a combination of one or more alkanes and/or cyclanes; HFC is a combination of one or more hydrofluorocarbon; and the adjuvant species is a combination of one or more fluorocarbon hydrocarbons. By means of combining a plurality of aerating powders and the assistance of the adjuvant, it is capable of obtaining a novel mixing foaming system, so as to obtain PU rigid foam with excellent combination property, especially PU rigid foam with excellent heat insulation performance.
Description
Technical field
The present invention relates to whipping agent, the whipping agent of a kind of PU of being used for rigid foam of more specifically saying so.
Background technology
The PU rigid foam is mainly used in the place that refrigerator, refrigerator, water-heater, heat supply pipeline etc. need adiabatic heat-insulation.The material that preparation PU hard bubbles has phenyl polyisocyanates (as MDI, TDI etc., being commonly called as black material), polyether glycol combination material (being commonly called as white material) and whipping agent etc.
For density is 35 ± 10Kg/M
3The PU rigid foam, wherein the PU matrix only accounts for about 3% of cumulative volume, and abscess accounts for cumulative volume about 97%.Foaming agent gas or foaming agent gas and mixtures of liquids abrim in the abscess, the composition of whipping agent and composition determine heat insulating ability and other performance of PU rigid foam to a great extent.
Be used for the environment-friendly foaming agent of PU rigid foam at present, mainly contain hydrocarbon polymer HC, as pentamethylene, Skellysolve A, iso-pentane, butane, Trimethylmethane etc., fluorinated hydrocarbon HFC, as HFC-245fa, HFC-365mfc, HFC-356mffm, HFC-134a and HFC-227ea etc., and fluorocarbon FC.Various whipping agents have characteristics separately, but any whipping agent of single use all can have defective.
Summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, the environment protection type high-efficiency multiple mixing aerating infusion that provides a kind of PU of being used for to hard bubble, by multiple whipping agent is made up, be aided with auxiliary agent again, to obtain new mixed foaming system, thereby obtain the PU rigid foam of excellent combination property, especially obtain to have the PU rigid foam of excellent insulation capacity.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics that the present invention is used for the environment protection type high-efficiency multiple mixing aerating infusion that PU hard bubbles are:
Its composition by weight: HC is that 5～15 parts, HFC are that 2～20 parts, auxiliary agent class are 0～10 part;
Described HC is the combination of one or more alkane and/or naphthenic hydrocarbon;
Described HFC is the combination of one or more hydrogen fluorohydrocarbons;
Described auxiliary agent class is the combination of one or more carbon fluorohydrocarbons.
The characteristics that the present invention is used for the environment protection type high-efficiency multiple mixing aerating infusion that PU hard bubbles also are:
Described whipping agent is following ternary mixed foaming system by weight:
HC is taken as 11 parts of pentamethylene, HFC, and to get HFC-365mfc be that 3.5 parts and HFC-245fa are 3.5 parts;
Or: HC is taken as 10 parts of pentamethylene, HFC, and to get HFC-356mffm be that 3 parts and HFC-245fa are 4 parts.
Described whipping agent is following quaternary mixed foaming system by weight:
HC is taken as 10 parts of pentamethylene, HFC, and to get HFC-365mfc be that 3 parts and HFC-245fa are that to get HFC-356mffm be 2 parts for 3 parts, auxiliary agent.
Described whipping agent is that following multiple mixing aerating foam is by weight:
The HC that is taken as 5～15 parts is one or more combinations in pentamethylene, Skellysolve A, iso-pentane, butane, the Trimethylmethane;
The HFC that is taken as 2～20 parts is HFC-365mfc or HFC-245fa or HFC-356mffm or HFC-365mfc and HFC-245fa or HFC-365mfc, HFC-245fa and HFC-356mffm;
The auxiliary agent that is taken as 0～10 part is FC, and described FC is perfluoro alkane or perfluoroolefine.
Contain HC, HFC and auxiliary agent in the mixed foaming system of the present invention, prepared hard PU foam can be used for the adiabatic heat-insulation of refrigerator or refrigerator etc., also can be used for other occasion, the foam that is used for refrigerator or refrigerator has ultralow thermal conductivity, high rate of closed hole and low density, after tested, its thermal conductivity≤18.5mW/mK, rate of closed hole 〉=93%, density≤32Kg/M
3, the abscess exquisiteness evenly, foam size is stable, stability to aging is good, produces the more energy-conservation and saving costs of household electrical appliance such as refrigerator/refrigerator with it.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, boiling point of the present invention is 28 ± 5 ℃ near room temperature, good manufacturability, and the combination material system vapor pressure that contains whipping agent is lower, and foaming machine need not big transformation;
2, the each component mutual solubility is good in the whipping agent of the present invention, and good with combination material intermiscibility, and particularly auxiliary agent also has solvability preferably in the whole system of whipping agent and combination material, thereby whole system has good stability in storage;
3, the feature of environmental protection of the present invention is good, ODP=0, low toxicity or nontoxic, the GWP value is very little;
4, the thermal conductivity of whipping agent gas phase of the present invention is lower, and the foamy adiabatic heat-insulation is good;
5, foaming system of the present invention has good flowability, and the demoulding cycle is short, can improve the production efficiency of foaming;
6, whipping agent of the present invention is little to plastic component corrodibility such as inner container of icebox, door end caps, can use the HIPS material;
7, among the present invention, batch mixing is the lower boiling component in proper order, fully is refrigerated to 0 ℃～5 ℃ earlier as HFC-245fa, takes out its liquid then, mixes being made into mixed foaming agent with other components, mix with the combination material again, thus Optimizing operation technology.
8, the present invention makes isocyanic ester and combination expect the ratio lower (1.15 ± 0.5) of (white material), and foam still has higher-strength.
Below pass through embodiment, and the invention will be further described in conjunction with the accompanying drawings:
Embodiment
Embodiment 1: ternary mixed foaming system
By weight, with 100 parts of polyether glycol consumptions, 130～135 parts of meters of polyisocyanates consumption, the mixed foaming agent system consists of:
3.5 parts of 10 parts of pentamethylene, 3.5 parts of HFC-365mfc and HFC-245fa
At first with HFC-245fa below 10 ℃ as frozen water in or fully place in 0 ℃ of freezer, take out liquid then by equivalent and HFC-365mfc thorough mixing, take out mixture more in proportion and mix with pentamethylene.
Taking by weighing quantitative mixed foaming agent and polyether glycol then fully mixes.
The process that is mixed of ternary mixed foaming agent also can be finished by the static mixer automatic gauge.This foaming system can be used for the thermal insulating warm-keeping layer hard polyurethane foam of refrigerator/refrigerator, and foam density is≤32Kg/M
3, thermal conductivity≤18.5mW/mK, the more single pentamethylene foaming of the energy consumption of refrigerator/refrigerator has remarkable reduction.This foaming system also can be used for hot duct insulation and building board, refrigerator car etc.
Embodiment 2: ternary mixed foaming system
By weight, with 100 parts of polyether glycol consumptions, 130～135 parts of meters of polyisocyanates consumption, the mixed foaming agent system consists of:
11 parts of pentamethylene, 7 parts of HFC-365mfc, FC (C
6F
14) 0.8 part
At first with HFC-365mfc and FC (C
6F
14) thorough mixing, take out mixture more in proportion and mix with pentamethylene.
Take by weighing quantitative mixed foaming agent and polyether glycol then and fully mix, all the other are with example 1.
Embodiment 3: ternary mixed foaming system
By weight, with 100 parts of polyether glycol consumptions, 130～135 parts of meters of polyisocyanates consumption, the mixed foaming agent system consists of:
11 parts of pentamethylene, 4 parts of HFC-365mfc, 3 parts of HFC-356mffm
At first HFC-365mfc and HFC-356mffm and pentamethylene etc. are mixed in proportion.
Take by weighing quantitative mixed foaming agent and polyether glycol then and fully mix, all the other are with example 1.
Embodiment 4: ternary mixed foaming system
By weight, with 100 parts of polyether glycol consumptions, 130～135 parts of meters of polyisocyanates consumption, the mixed foaming agent system consists of:
10 parts of pentamethylene, 6 parts of HFC-245fa, FC (C
6F
12) 0.6 part
At first with HFC-245fa below 10 ℃ as frozen water in or fully place in 0 ℃ of freezer, take out liquid then and mix with pentamethylene in proportion, again with FC (C
6F
12) mix, all the other are with example 1.
Embodiment 5: quaternary mixed foaming system
By weight, with 100 parts of polyether glycol consumptions, 130～135 parts of meters of polyisocyanates consumption, the mixed foaming agent system consists of:
12 parts of pentamethylene, 2.5 parts of 2.5 parts of HFC-365mfc, HFC-245fa, FC (C
6F
12) 0.5 part
At first with HFC-245fa below 10 ℃ as frozen water in or fully place in 0 ℃ of freezer, take out liquid then and mix with HFC-365mfc in proportion, pentamethylene mixing again, FC (C
6F
12) mix, all the other are with example 1.
Embodiment 6: multiple mixing aerating foam system
By weight, with 100 parts of polyether glycol consumptions, 130～135 parts of meters of polyisocyanates consumption, the mixed foaming agent system consists of:
6 parts of iso-pentane, 6 parts of pentamethylene, 3 parts of 2 parts of HFC-365mfc, HFC-245fa, FC (C
6F
14) 0.5 part
At first with HFC-245fa below 10 ℃ as frozen water in or fully place in 0 ℃ of freezer, take out liquid then and mix with HFC-365mfc in proportion, mix with other again, all the other are with example 1.
Each components selection scope relates generally to:
Classification: comprise C
4～C
5The HC of alkane and naphthenic hydrocarbon mainly is pentamethylene, pentane, iso-pentane, butane, Trimethylmethane etc.; Hydrogen fluorohydrocarbon HFC mainly is HFC-365mfc, HFC-245fa, HFC-134a, HFC-152a, HFC-356mffc etc.; The auxiliary agent class is FC, mainly has been efficient nucleogenesis, adjusts cell size and homogeneity, as C
5F
12, C
6F
14, C
6F
12, C
9F
18Deng.
The mixing of each component is adopted and is divided manual batch mixing, mechanical batch mixing and semi-hand half mechanical batch mixing to combine.When manual batch mixing, just operate the boiling point junior according to the boiling point of each component, as below room temperature, need to treat that prior in the frozen water or carry out fully freezingly below 10 ℃ in the cryostat temperature of charge reduces to below the boiling point, suggestion is low more than 10 ℃ than boiling point, and row is got the material mixing again.As HFC-245fa, must be in frozen water or 0 ℃ and following freezer in fully place after, just desirablely go out liquid.
The present invention is applicable to that mainly with polyether glycol or the pure and mild polyisocyanates of polyester polyols (as MDI, thick MDI, PAPI, TDI or its composition) be the hard polyurethane foams foaming system of base-material, household electrical appliance series products adiabatic heat-insulations such as this hard polyurethane foams particularly suitable refrigerator, refrigerator-freezer, water-heater, electric cooker, also can be used for refrigerating equipment such as refrigerator car, frozen products insulated container, basin, freezer etc., can also be used for industrial equipments and pipe insulation, building construction, structured material such as sheet material, sandwich panel etc.
Claims (4)
1. be used for the environment protection type high-efficiency multiple mixing aerating infusion that PU hard bubbles, it is characterized in that:
Its composition by weight: HC is that 5～15 parts, HFC are that 2～20 parts, perfluoroolefine are 0～10 part, and the amount of wherein said perfluoroolefine is not 0;
Described HC is the combination of one or more alkane and/or naphthenic hydrocarbon;
Described HFC is the combination of one or more hydrogen fluorohydrocarbons.
2. the environment protection type high-efficiency multiple mixing aerating infusion that the PU of being used for according to claim 1 hard bubbles is characterized in that described whipping agent is following ternary mixed foaming system by weight:
HC is taken as 10 parts of pentamethylene, HFC, and to get HFC-245fa be 6 parts, and perfluoroolefine is got C
6F
12It is 0.6 part.
3. the environment protection type high-efficiency multiple mixing aerating infusion that the PU of being used for according to claim 1 hard bubbles is characterized in that described whipping agent is following quaternary mixed foaming system by weight:
HC is taken as 12 parts of pentamethylene, HFC, and to get HFC-365mfc be that 2.5 parts and HFC-245fa are that 2.5 parts, perfluoroolefine are got C
6F
12It is 0.5 part.
4. the environment protection type high-efficiency multiple whipping agent that the PU of being used for according to claim 1 hard bubbles is characterized in that: described perfluoroolefine is C
6F
12Or C
9F
18
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101168189A CN101550241B (en) | 2009-05-19 | 2009-05-19 | Environment protection type high-efficiency multiple mixing aerating powder for PU rigid foam |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101168189A CN101550241B (en) | 2009-05-19 | 2009-05-19 | Environment protection type high-efficiency multiple mixing aerating powder for PU rigid foam |
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| CN101550241A CN101550241A (en) | 2009-10-07 |
| CN101550241B true CN101550241B (en) | 2011-10-05 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101132774B1 (en) * | 2009-07-06 | 2012-04-06 | 수경화학 주식회사 | A blowing agent for insulating material, foam composition comprising the same, and preparation method of foam using the same |
| CN102050957B (en) * | 2009-10-30 | 2015-12-02 | 霍尼韦尔国际公司 | The Azeotrope-like compositions of 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-3-pentafluorobutane and pentamethylene |
| BR112014015179A8 (en) * | 2011-12-19 | 2017-07-04 | Honeywell Int Inc | composition, blowing agent and foaming composition |
| CN104045847A (en) * | 2013-12-17 | 2014-09-17 | 中集集团集装箱控股有限公司 | Foaming agent composition, foaming body composition and foaming body preparation method |
| CN106397709A (en) * | 2016-09-05 | 2017-02-15 | 珠海格力电器股份有限公司 | Polyurethane foaming composition, polyurethane foaming process and water heater |
| CN110105520B (en) * | 2019-05-05 | 2021-09-21 | 深圳市盈石科技有限公司 | Heat-insulating rigid polyurethane foam and preparation method thereof |
| CN110396213B (en) * | 2019-08-22 | 2022-02-25 | 长虹美菱股份有限公司 | Polyurethane heat-insulating layer for refrigerator and preparation method thereof |
| CN116285306B (en) * | 2023-05-24 | 2023-08-18 | 北京宇极科技发展有限公司 | Foaming composition, polyurethane foam and preparation method thereof |
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| C56 | Change in the name or address of the patentee |
Owner name: HEFEI MIDEA REFRIGERATOR CO., LTD. Free format text: FORMER NAME: HEFEI MEDIA RONGSHIDA REFRIGERATOR CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 230088 No. 669 Changjiang West Road, Shushan District, Anhui, Hefei Patentee after: Hefei Midea Refrigerator Co., Ltd. Address before: 230088 No. 669 Changjiang West Road, Shushan District, Anhui, Hefei Patentee before: Hefei Media Rongshida Refrigerator Co., Ltd. |