CN103275296B - Polyurethane foam for wet-method preparation and preparation method thereof - Google Patents
Polyurethane foam for wet-method preparation and preparation method thereof Download PDFInfo
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Abstract
The invention relates to polyurethane foam for wet-method preparation and a preparation method thereof, and belongs to the field of polyurethane foam production. The polyurethane foam is used for wet-method preparation of an automobile skylight sun shield or an automobile top. The polyurethane foam comprises a material A composed of polyether polyol, glycerin, silicone oil, water, a catalyst 1, a reaction catalyst 2, a low-volatility catalyst, an opening agent, and an anti-oxidant, and also comprises a material B composed of a mixture of pure MDI or polymerized MDI and MDI. The material A and the material B are mixed according to the above ratio and then are foamed to form the polyurethane foam for wet-method preparation of an automobile skylight sun shield or an automobile top. The preparation method is mainly used for a foaming continuous-production line. The preparation method is suitable for large-scale multi-size production. The more yield is, the higher foaming rate is. The preparation method has the advantages that in the industry, it is recognized that continuous foaming and box type foaming have the advantages of high foaming quality, accurate raw material metering, and uniform foam apertures; difference of upper, middle and lower parts of the foam block is reduced; unavailable upper and lower parts of the foam block can be controlled; and through multiple top flattening technologies, a foam yield is improved.
Description
Technical field
The present invention relates to a kind of wet-layer preparation polyurethane foam and preparation method thereof, this polyurethane foam is mainly used in wet method automobile skylight sun-shield and top is produced, and belongs to polyurethane foam production field.
Background technology
Polyurethane foam is applied extremely extensive in life, and in the various parts, particularly inside gadget that manufacture automobile, the foam materials of urethane occupies critical role.The dormer window sunshading board of automobile and the wet-layer preparation of top just have employed partly hard bubbling of urethane.Polyurethane semihard foam is compounded to form automotive sunshade panel or top at about 130 DEG C under the mould pressurizeed with glass and glued membrane and non-woven fabrics under the effect of polyurethane binder.This technique can be automobile factory and provides the product meeting rigidity and service requirements, as the dimensional stability etc. of ductility, resistance to environmental testing.
Due to the uniqueness that each vehicle designs, the mould extensibility of the automobile skylight sun-shield that every money vehicle is corresponding and top is all different, therefore requires very high to the toughness of polyurethane foam and forming stability; And dormer window sunshading board can improve the requirement of the suction glue amount to polyurethane foam equally to the unique requirements of rigidity.
Along with automotive industry and social development, what automobile industry required is not only the sun visor or the top that meet fundamental property, and requiring that product also possesses lightweight while meeting fundamental property more and more, low volatilization, low smell also has the environment-friendly advantages such as good sound absorption qualities.Currently marketed like product all has certain limitation to the requirement meeting automobile industry, as high in rate of closed hole etc., cause sound absorption qualities cannot meet main engine plants' requirement.
The froth product for automobile wet method sun visor or top used on the market is all complete by the production technique of box foaming, and the method investment is little, is suitable for simplification product and application in a small amount.Such as, under mould and artificial sufficient condition, it has been high-level efficiency that average per half an hour produces a bubble block, and that is per tour workman can produce 12-16 bubble block.
Summary of the invention
Object of the present invention is producing a kind of polyurethane foam for automobile wet-layer preparation dormer window sunshading board and top, this foam adopt ODS be zero full water foamed, percentage of open area is high, and can carry out continuous prodution or box foaming.This foam can meet light weight, low smell, and shaping unit elongation is high, and shaping suction glue amount is high, and has good sound absorption qualities.The production technique that foam is taked has broken the poor efficiency of traditional box foam process, is particularly suitable for large-scale industrial production, and the stability of product is also improved simultaneously.
According to technical scheme provided by the invention, a kind of wet-layer preparation polyurethane foam, formula rate is as follows by weight:
A expects: polyether glycol 100 parts, glycerine 0.5-5 part, silicone oil 0.5-2 part, water 3.5-5.5 part, catalyzer 1 0.2-1.0 part, active catalyst 2 0.1-0.5 part, low-volatility catalyst 0.01-0.2 part, pore-creating agent 0.1-2 part, oxidation inhibitor 0.1-1.0 part;
B expects: the mixture of pure MDI or polymeric MDI and MDI 50-90:50-10 ratio;
The ratio of the hydroxyl equivalent during isocyanurate equivalent and A contained by described B material expect is 1-1.25;
Namely obtain product after above-mentioned A material and B material are mixed in proportion foaming and be used for wet-layer preparation automobile skylight sun-shield or automobile calash polyurethane foam.
Described polyether glycol is composed as follows:
Polyethers A, carbohydrate or sorbyl alcohol or glycerine, hydroxyl value 450-650,10-30 part;
Polyethers B, phthalic anhydride kind polyester polyethers, hydroxyl value 200-350,5-35 part;
Polyethers C, the polyethers of glycerin polyether, hydroxyl value 28-35,10-40 part;
Polyethers D, chainextender, hydroxyl value 56-160,10-35 part;
One in polyethers E, 3-30 part crude soya bean polyethers, plam oil polyether glycol or polyether, hydroxyl value 20-56;
Polyethers F, 1-10 part diamines polyethers, hydroxyl value 450-800;
Polyethers G, glycerine, hydroxyl value 160-240,10-30 part.
Described polyether glycol also comprises the biological polyethers of 1-30 part, the one namely in soybean oils or palmitic acid oils polyethers.
Described catalyzer 1 is tertiary amine, is specially the one in HUNTSMAN Jeffcat ZF10, ZR50, Jeffcat DFA or Dabaco NE300; Described active catalyst 2 is DMEA; Described low-volatility catalyst is stannous octoate, and model is T10, T9, T12 etc.
Described chainextender is the low molecular polyether of 2 functionality, and hydroxyl value is 56-300mgKOH/g.
The proportion of primary OH groups of described polyethers is greater than 70%.
Described oxidation inhibitor is PUR 68, Irganox (R) 1135, Irganox (R) 1076 or the A01 purchased from Air Products Company purchased from BASF AG.
Described pore-creating agent is purchased from the Ortegol 501 of Air Products Company, GLK-15 or GK-350D purchased from Gaoqiao Petrochemical Company.
The preparation method of described wet-layer preparation polyurethane foam, be applicable to continuous lines foam production mode or the box foaming of intermittent type, step is as follows:
(1) configuration of part A material: get polyether glycol 100 parts, glycerine 0.5-5 part, pore-creating agent 0.1-2 part, oxidation inhibitor 0.1-1.0 part, drop into agitator premix, agitator speed is 10-20rpm/min, and mixing time is 50-70min, obtains premix A and expects;
(2) preparation of B material: B material is the mixture of pure MDI or polymeric MDI and MDI 50-90:50-10 ratio, squeezes into another equally and produces batch can, keeps feed temperature to maintain 20-24 DEG C;
(3) preparation of other A material: get silicone oil 0.5-2 part, water 3.5-5.5 part is placed in batch can respectively, gets catalyzer 1 0.2-1.0 part, active catalyst 2 0.1-0.5 part, and low-volatility catalyst 0.01-0.2 part all adds in a batch can, stand-by;
(4) tinuous production foaming: the A material that premix A step (1) prepared expects and silicone oil, water, catalyzer form and B material are metered into mixing system foaming respectively by high-low pressure volume pump; The ratio of the hydroxyl equivalent during isocyanurate equivalent and A contained by wherein in B material expect is 1-1.25; Stirring velocity after feed liquid enters mixing head controls at 1000-5000rpm/min, and line speed is 3-7m/min;
By adjusting foaming quality and all whole degree of bubble block of preposition lifter plate rate-determining steps (3); Foam continuous seepage starts to carry out cutting on line and on-line tuning product width according to size afterwards;
(5) slaking: the bubble block after being cut by step (3) gained, after slaking in 44-52 hour, obtains product wet-layer preparation polyurethane foam;
Or directly the A configured material and B material are foamed on box foaming line.
The percentage of open area of foam is greater than 90%, is conducive to improving the suction glue amount of foam and the sound absorption qualities of ceiling goods.
Its catalyzer refers to active catalyst, in polyurethane foam preparation, participate in chemical reaction, not residual low molecular weight volatile thing.
Tool of the present invention has the following advantages: the present invention is mainly used in continuous foamed production line, and the box explained hereafter amount of a day only with race 20 minutes, also can convert product size aborning in continuous lines.This technique is applicable in enormous quantities, many sizes and produces very much, and foaming line manually with other posies and use, can improve production efficiency effectively.In addition, output is larger, and blebbing rate is higher.Steeping block, advantage is more qualitatively in the continuous foamed and box foaming of generally acknowledging in industry, and raw material metering is accurate, uniform foam cell; Bubble block upper, middle and lower difference reduces; Bubble block top and bottom unavailable part are controlled; Multiple flat-top technology can be adopted to improve blebbing rate etc.
Embodiment
Embodiment 1
(1) configuration of part A material: get polyether glycol 100 parts, glycerine 0.5 part, pore-creating agent 0.1 part, 0.1 part, oxidation inhibitor, drop into agitator premix, agitator speed is 10rpm/min, and mixing time is 50min, obtains premix A and expects;
Described polyether glycol is composed as follows:
Polyethers A, carbohydrate or sorbyl alcohol or glycerine, hydroxyl value 450,10 parts;
Polyethers B, phthalic anhydride kind polyester polyethers, hydroxyl value 200,5 parts;
Polyethers C, the polyethers of glycerin polyether, hydroxyl value 28,10 parts;
Polyethers D, chainextender, hydroxyl value 56,10 parts;
Polyethers E, 3 parts of crude soya bean polyethers, hydroxyl value 20;
Polyethers F, 1 part of diamines polyethers, hydroxyl value 450;
Polyethers G, glycerine, hydroxyl value 160,10 parts.
Described polyether glycol also comprises soybean oils 1 part.
(2) preparation of B material: B material is the mixture of pure MDI or polymeric MDI and MDI 50:50 ratio, squeezes into another equally and produces batch can, keeps feed temperature to maintain 20 DEG C;
(3) preparation of other A material: get silicone oil 0.5 part, 3.5 parts, water is placed in batch can respectively, gets catalyzer 1 0.2 parts, active catalyst 2 0.1 parts, low-volatility catalyst 0.01 part, all adds in a batch can, stand-by;
(4) tinuous production foaming: the A material that premix A step (1) prepared expects and silicone oil, water, catalyzer form and B material are metered into mixing system foaming respectively by high-low pressure volume pump; The ratio of the hydroxyl equivalent during isocyanurate equivalent and A contained by wherein in B material expect is 1; Stirring velocity after feed liquid enters mixing head controls at 5000rpm/min, and line speed is 3m/min;
By adjusting foaming quality and all whole degree of bubble block of preposition lifter plate rate-determining steps (3); Foam continuous seepage starts to carry out cutting on line and on-line tuning product width according to size afterwards;
(5) slaking: the bubble block after being cut by step (3) gained, after slaking in 44 hours, obtains product wet-layer preparation polyurethane foam.
Described catalyzer 1 is tertiary amine, is specially HUNTSMAN Jeffcat ZF10; Described active catalyst 2 is DMEA; Described low-volatility catalyst is stannous octoate, and model is T10.
Described pore-creating agent is PUR 68.
Described oxidation inhibitor is Ortegol 501.
Embodiment 2
(1) configuration of part A material: get polyether glycol 100 parts, glycerine 5 parts, pore-creating agent 2 parts, 1.0 parts, oxidation inhibitor, drop into agitator premix, agitator speed is 20rpm/min, and mixing time is 70min, obtains premix A and expects;
Polyethers A, glycerine, hydroxyl value 650,30 parts;
Polyethers B, phthalic anhydride kind polyester polyethers, hydroxyl value 350,35 parts;
Polyethers C, the polyethers of glycerin polyether, hydroxyl value 35,40 parts;
Polyethers D, chainextender, hydroxyl value 160,35 parts;
Polyethers E, the one in 30 parts of crude soya bean polyethers, plam oil polyether glycol or polyethers, hydroxyl value 56;
Polyethers F, 10 parts of diamines polyethers, hydroxyl value 800;
Polyethers G, glycerine, hydroxyl value 240,30 parts.
(2) preparation of B material: B material is the mixture of pure MDI or polymeric MDI and MDI 90:10 ratio, squeezes into another equally and produces batch can, keeps feed temperature to maintain 24 DEG C;
(3) preparation of other A material: get silicone oil 2 parts, 5.5 parts, water is placed in batch can respectively, gets catalyzer 1 1.0 parts, active catalyst 2 0.5 parts, low-volatility catalyst 0.2 part, all adds in a batch can, stand-by;
(4) tinuous production foaming: the A material that premix A step (1) prepared expects and silicone oil, water, catalyzer form and B material are metered into mixing system foaming respectively by high-low pressure volume pump; The ratio of the hydroxyl equivalent during isocyanurate equivalent and A contained by wherein in B material expect is 1.25; Stirring velocity after feed liquid enters mixing head controls at 5000rpm/min, and line speed is 7m/min;
By adjusting foaming quality and all whole degree of bubble block of preposition lifter plate rate-determining steps (3); Foam continuous seepage starts to carry out cutting on line and on-line tuning product width according to size afterwards;
(5) slaking: the bubble block after being cut by step (3) gained, after slaking in 52 hours, obtains product wet-layer preparation polyurethane foam.
Described catalyzer 1 is tertiary amine, is specially HUNTSMAN Jeffcat ZR50; Described active catalyst 2 is DMEA; Described low-volatility catalyst is stannous octoate, and model is T9.
Described pore-creating agent is Irganox 1135.
Described oxidation inhibitor is GLK-15.
Embodiment 3
(1) configuration of part A material: get polyether glycol 100 parts, glycerine 0.5-5 part, pore-creating agent 0.1-2 part, oxidation inhibitor 0.1-1.0 part, drop into agitator premix, agitator speed is 10-20rpm/min, and mixing time is 50-70min, obtains premix A and expects;
Polyethers A, sorbyl alcohol, hydroxyl value 500,20 parts;
Polyethers B, phthalic anhydride kind polyester polyethers, hydroxyl value 300,20 parts;
Polyethers C, the polyethers of glycerin polyether, hydroxyl value 30,25 parts;
Polyethers D, chainextender, hydroxyl value 100,20 parts;
Polyethers E, 15 parts of plam oil polyether glycols, hydroxyl value 30;
Polyethers F, 6 parts of diamines polyethers, hydroxyl value 600;
Polyethers G, glycerine, hydroxyl value 200,20 parts.
(2) preparation of B material: B material is the mixture of pure MDI or polymeric MDI and MDI 50-90:50-10 ratio, squeezes into another equally and produces batch can, keeps feed temperature to maintain 20-24 DEG C;
(3) preparation of other A material: get silicone oil 0.5-2 part, water 3.5-5.5 part is placed in batch can respectively, gets catalyzer 1 0.2-1.0 part, active catalyst 2 0.1-0.5 part, and low-volatility catalyst 0.01-0.2 part all adds in a batch can, stand-by;
(4) tinuous production foaming: the A material that premix A step (1) prepared expects and silicone oil, water, catalyzer form and B material are metered into mixing system foaming respectively by high-low pressure volume pump; The ratio of the hydroxyl equivalent during isocyanurate equivalent and A contained by wherein in B material expect is 1-1.25; Stirring velocity after feed liquid enters mixing head controls at 1000-5000rpm/min, and line speed is 3-7m/min;
By adjusting foaming quality and all whole degree of bubble block of preposition lifter plate rate-determining steps (3); Foam continuous seepage starts to carry out cutting on line and on-line tuning product width according to size afterwards;
(5) slaking: the bubble block after being cut by step (3) gained, after slaking in 44-52 hour, obtains product wet-layer preparation polyurethane foam;
Or directly the A configured material and B material are foamed on box foaming line.
Described catalyzer 1 is tertiary amine, is specially Jeffcat DFA; Described active catalyst 2 is DMEA; Described low-volatility catalyst is stannous octoate, and model is T12.
Described pore-creating agent is Irganox 1076.
Described oxidation inhibitor is GK-350D.
* contained hydroxyl equivalent number in all polyethers and all additives in isocyanate group reaction equivalent number in index=B material/A material
Reaction equivalent number=reactant weight/reactant equivalent
Isocyanate reaction equivalents=isocyanate weight/(NCO molecular weight/NCO% x100)
Hydroxyl reaction equivalents=polyethers weight/(56100/ hydroxyl value)
Conventional continuous foamed line essentially consist is as follows: computerized control system, constant temperature storage tank, Preblend system, online raw material temperature control system (heat exchanger etc.), accurate raw material metering pump system, mixing head system, foaming production line, online foam diced system.
Claims (2)
1. a wet-layer preparation polyurethane foam, is characterized in that formula rate is as follows by weight:
A expects: polyether glycol 100 parts, glycerine 0.5-5 part, silicone oil 0.5-2 part, water 3.5-5.5 part, catalyzer 1 0.2-1.0 part, active catalyst 2 0.1-0.5 part, low-volatility catalyst 0.01-0.2 part, pore-creating agent 0.1-2 part, oxidation inhibitor 0.1-1.0 part;
B expects: the mixture of pure MDI or polymeric MDI and MDI 50-90:50-10 ratio;
The ratio of the hydroxyl equivalent during isocyanurate equivalent and A contained by described B material expect is 1-1.25;
Namely obtain product after above-mentioned A material and B material are mixed in proportion foaming and be used for wet-layer preparation automobile skylight sun-shield or automobile calash polyurethane foam;
Described polyether glycol is composed as follows:
Polyethers A, by carbohydrate or sorbyl alcohol or glycerine initial, hydroxyl value 450-650,10-30 part;
Polyethers B, phthalic anhydride kind polyester polyethers, hydroxyl value 200-350,5-35 part;
Polyethers C, glycerin polyether, hydroxyl value 28-35,10-40 part;
Polyethers D, chainextender, hydroxyl value 56-160,10-35 part;
One in polyethers E, 3-30 part crude soya bean polyethers, plam oil polyether glycol or polyether, hydroxyl value 20-56;
Polyethers F, 1-10 part diamines polyethers, hydroxyl value 450-800;
Polyethers G, initial by glycerine, hydroxyl value 160-240,10-30 part;
2. the preparation method of wet-layer preparation polyurethane foam described in claim 1, is characterized in that step is as follows:
(1) configuration of part A material: get polyether glycol 100 parts, glycerine 0.5-5 part, pore-creating agent 0.1-2 part, oxidation inhibitor 0.1-1.0 part, drop into agitator premix, agitator speed is 10-20rpm/min, and mixing time is 50-70min, obtains premix A and expects;
(2) preparation of B material: B material is the mixture of pure MDI or polymeric MDI and MDI 50-90:50-10 ratio, squeezes into another equally and produces batch can, keeps feed temperature to maintain 20-24 DEG C;
(3) preparation of other A material: get silicone oil 0.5-2 part, water 3.5-5.5 part is placed in batch can respectively, gets catalyzer 1 0.2-1.0 part, active catalyst 2 0.1-0.5 part, and low-volatility catalyst 0.01-0.2 part all adds in a batch can, stand-by;
(4) tinuous production foaming: other A that premix A step (1) prepared expects and silicone oil, water, catalyzer form expects and B material is metered into mixing system foaming respectively by high-low pressure volume pump; The ratio of the hydroxyl equivalent during isocyanurate equivalent and A contained by wherein in B material expect is 1-1.25; Stirring velocity after feed liquid enters mixing head controls at 1000-5000rpm/min, and line speed is 3-7m/min;
By adjusting foaming quality and all whole degree of bubble block of preposition lifter plate rate-determining steps (4); Foam continuous seepage starts to carry out cutting on line and on-line tuning product width according to size afterwards;
(5) slaking: the bubble block after being cut by step (4) gained, after slaking in 44-52 hour, obtains product wet-layer preparation polyurethane foam.
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| CN104086747A (en) * | 2014-07-11 | 2014-10-08 | 无锡吉兴木桥高分子材料科技有限公司 | Lightweight polyurethane foam for automobile roof and preparation method of lightweight polyurethane foam |
| CN105418882A (en) * | 2015-12-21 | 2016-03-23 | 重庆金杯汽车配件有限责任公司 | Car environment-friendly interior polyurethane combined material |
| CN107501516A (en) * | 2017-09-08 | 2017-12-22 | 张家港长泰汽车饰件材料有限公司 | Low aldehyde content polyurethane plate and preparation method thereof |
| PT3720893T (en) | 2017-12-08 | 2021-09-02 | Shell Int Research | Antioxidant for low-density polyurethane foam |
| CN108373529A (en) * | 2018-02-13 | 2018-08-07 | 无锡吉兴木桥高分子材料科技有限公司 | Automobile dry method ceiling polyurethane foam and preparation method thereof |
| CN109535381A (en) * | 2018-12-06 | 2019-03-29 | 上海应用技术大学 | A kind of manufacture craft of low VOC polyurethane automobile instrument board |
| CN109666112A (en) * | 2018-12-12 | 2019-04-23 | 无锡吉兴木桥高分子材料科技有限公司 | A kind of roof of the vehicle polyurethane foam and preparation method thereof |
| CN109593181A (en) * | 2018-12-12 | 2019-04-09 | 怀化学院 | Polyurethane foam and preparation method thereof |
| CN109776758A (en) * | 2018-12-25 | 2019-05-21 | 无锡吉兴木桥高分子材料科技有限公司 | A kind of automobile engine sound insulation pad polyurethane foam and preparation method thereof |
| CN110105526A (en) * | 2019-05-22 | 2019-08-09 | 吴聚精 | A kind of green plants organic environmental-protection foam and its production technology |
| EP4059971A1 (en) | 2021-03-17 | 2022-09-21 | Covestro Deutschland AG | Method for the continuous production of low density and high elongation polyurethane foams |
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Address after: 214191 No. 322 Youyi North Road, Xishan Economic Development Zone, Wuxi City, Jiangsu Province Patentee after: Wuxi Jixing polymer material technology Co.,Ltd. Patentee after: XANATHANE SYSTEMS SHANGHAI Co.,Ltd. Address before: 214191 No. 322 Youyi North Road, Xishan Economic Development Zone, Wuxi City, Jiangsu Province Patentee before: PROPRIETECT LLP Patentee before: XANATHANE SYSTEMS SHANGHAI Co.,Ltd. |
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| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210901 Address after: 214191 friendship north road, Xishan Economic Development Zone, Jiangsu, Wuxi 322, China Patentee after: WUXI JIXING AUTO PARTS Co.,Ltd. Address before: 214191 No. 322 Youyi North Road, Xishan Economic Development Zone, Wuxi City, Jiangsu Province Patentee before: Wuxi Jixing polymer material technology Co.,Ltd. Patentee before: XANATHANE SYSTEMS SHANGHAI Co.,Ltd. |