CN1140584C - Heat-resisting foamed polyurethane plastics - Google Patents
Heat-resisting foamed polyurethane plastics Download PDFInfo
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- CN1140584C CN1140584C CNB001370537A CN00137053A CN1140584C CN 1140584 C CN1140584 C CN 1140584C CN B001370537 A CNB001370537 A CN B001370537A CN 00137053 A CN00137053 A CN 00137053A CN 1140584 C CN1140584 C CN 1140584C
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- foamed polyurethane
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Abstract
The present invention discloses high-temperature resistant foamed polyurethane plastics. Silicone resin is coated on polyaminoester foamed plastics by a roll coating method, a knife coating method or a spraying method, and then, the silicone resin is solidified to manufacture the high-temperature resistant foamed polyurethane plastics. The heat temperature resistant range of material is from 180 to 220 DEG C, the apparent density is from 0.15 to 0.50 g/cm<3>, and the content of silicone resin is from 75 to 90% by weight.
Description
The present invention relates to a kind of high temperature resistant poly-hydrogen ester porous plastics, particularly, the present invention relates on urethane foam, be coated with silicone resin, the heat-resisting foamed polyurethane plastics that makes after the curing.
Urethane foam is divided into polyester type and polyether-type.The volume density of the open pore polyurethane porous plastics that market can be buied is at the 0.03-0.04 gram per centimeter
3Scope.This elastic properties of materials height, intensity is big, but temperature resistant grade is low, generally degraded about 140 ℃.
What temperature resistant grade was the highest in the organic foam plastic is the organosilicon sponge, and temperature resistant range is generally 200-300 ℃ of scope.United States Patent (USP) 6,096,792 disclose as the organo-silicone rubber sponge composite, and smooth by the sponge top layer that this composition forms, the surface is inviscid, has good weathering resistance, electrical property and compression set.Said composition comprises mean polymerisation degree 3,000-300,000 organopolysiloxane, strengthen the silica filler of usefulness, as 1 of whipping agent, 1 '-azo-two (1-acetoxyl group-1-diphenylphosphino ethane) and solidifying agent.United States Patent (USP) 4,391,921 disclose a kind of method of making the silicone elastomer sponge, and this method comprises freezing moisture organic silicon emulsion, melts then and drying, makes the organosilicon sponge that contains irregular closed pore.This emulsion comprises water, stable hydroxy-end capped polydiorganosiloxane, organo-tin compound and the colloidal silica of negatively charged ion.Isolator and sealing material when the silicone elastomer sponge of making can be used for high temperature and low temperature.
Organosilicon sponge excellent property, but cost is very high, and its application is restricted.In recent years, people attempt to come modified polyurethane material by the whole bag of tricks.United States Patent (USP) 4,323,656 disclose a kind of polyurethane sponge that is dispersed with additive.These additives comprise washing lotion, washing composition, sterilant, silicone oil etc.In the presence of catalyzer, polyethers or polyester and isocyanic ester, additive reaction form sponge structure, and additive is trapped within the space of sponge.The polyurethane sponge of making has high liquid absorption capacity, and has good hand feeling.These class methods mostly are to add various additives in polyurethane foam combination, foam then.When selecting additive, must consider the influence when additive reacts foam composition, and to the porous plastics Effect on Performance.
According to the purposes of product, in the shape that urethane foam is cut into requirement, during as rectangular parallelepiped, right cylinder, semi-circular ring etc.Because lower grade of urethane heatproof, generally can adopt nichrome wire cutting.Before the cutting,, nichrome wire is made different shape according to the shape need of product.
The organosilicon sponge material generally can not cut with nichrome wire because its heatproof upper limit can reach 200-300 ℃, and to requiring the application of complicated shape, its cutting is difficulty.
The purpose of this invention is to provide a kind of heat-resisting foamed polyurethane plastics.
Heat-resisting foamed polyurethane plastics of the present invention is to adopt print roll coating, scraper coating or spraying method, is cutting, and to requiring the application of complicated shape, its cutting is difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of heat-resisting foamed polyurethane plastics.
Heat-resisting foamed polyurethane plastics of the present invention is to adopt print roll coating, scraper coating or spraying method, is coated with organosilicon resin composition on urethane foam, solidifies then and makes.The heat-resisting foamed polyurethane plastics heat resisting temperature of making can be brought up to 180-220 ℃ of scope, and volume density reaches the 0.15-0.50 gram per centimeter
3, silicone resin content is 75-90% (weight), has still kept cavernous structure, elasticity, ventilation property and the intensity of urethane foam simultaneously.
Among the present invention, be the deep layer that makes silicone resin can immerse porous plastics, generally select the open pore polyurethane porous plastics for use.The organosilicon resin composition of coating usefulness comprises: 100 weight part silicone resins, 2-6 weight part catalyzer, 4-10 weight part solidifying agent, 10-20 weight part toughener, 0-10 weight part tinting material, 0-100 parts by weight diluent.
Herein, " silicone resin " refers to comprise the organosilicon resin composition of all components except thinner." silicone resin content " calculates according to following formula:
Silicone resin content=[(the organosilicon resin composition weight-dilution dosage that is coated with on the unit volume urethane foam)/make unit volume urethane foam weight] * 100
Silicone resin is selected for use under the room temperature and to be the silicone resin of liquid.Condition during according to curing is divided into two classes, i.e. room temperature curing type (RTV) silicone resin and heat-curing type (LSR) silicone resin.Catalyzer commonly used is a dibutyl tin laurate; Solidifying agent commonly used has tetraethoxy, amine curing agent etc.; Tinting material commonly used has titanium dioxide, phthalocyanine blue, red iron oxide etc.; Toughener has gas-phase silica, barium sulfate, upright powder etc.; For adjusting the viscosity of solution, can add thinner in the organosilicon resin composition, as silicone oil, alkane wet goods.
In organosilicon resin composition, also can add heat resistance accessory, fire retardant etc., further the character of modified rigid polyurethane foam.As in organosilicon resin composition, adding the fire retardant of 15-20 weight part, as weisspiessglanz, zinc borate, decabromodiphynly oxide etc., make urethane foam not only can tolerate certain high temperature, also can possess certain flame retardant resistance.
When making heat-resisting foamed polyurethane plastics, cut common open pore polyurethane porous plastics at first on request; With organosilicon resin composition dipping, can adopt ordinary method to handle urethane foam again, be coated with or method such as spraying as print roll coating, scraper.According to silicone resin content, temperature resistant range and the density of the finished product, select treatment process, for example, when requiring the silicone resin amount higher, the viscosity of general solution is higher, can adopt print roll coating or scraper coating method, by regulating the gap of roll gap or scraper, control glue spread; When requiring the silicone resin amount low, for ease of control, can add an amount of thinner in organosilicon resin composition, this moment, the concentration and the viscosity of solution were all lower, can adopt spraying method.Urethane foam after the coating by two rollers or multiple roll, is regulated the pressure that is applied on the roller continuously, makes the solution of top step coating infiltrate internal layer from the top layer, strengthens dipping effect; Silicone resin in the final curing porous plastics makes resistant to elevated temperatures urethane foam.
The porous plastics that makes according to the described method of GB 7759-1996, is measured the static compression distortion after room temperature is placed 3 days, the deformation values of heat-resisting foamed polyurethane plastics of the present invention is 0.
With containing organic silicon resin composition dipping open pore polyurethane porous plastics, silicone resin can be coated on the hole wall of urethane foam, makes urethane foam possess the thermotolerance of silicone resin, improves the degradation temperature of urethane foam.
Heat-resisting foamed polyurethane plastics of the present invention can be used for the various uses of use under the requirement high temperature, as the high temperature resistant bedding and padding that making up plant's whole ironing equipment is used, carries high-temperature material pipe insulation material etc.
Compare with common urethane foam, heat-resisting foamed polyurethane plastics heat resisting temperature of the present invention and density improve greatly, and heat resisting temperature can reach 180-220 ℃, and volume density reaches the 0.15-0.50 gram per centimeter
3Static compression after under the 30-70% rate of compression 72 hours is deformed into 0.With carry out foamable reaction at foaming composition before add the modified rigid polyurethane foam that additive makes and compare, the method that the present invention adopts is a kind of physical treatment method, needn't consider the influence of silicone resin to foamable reaction.Compare with the organosilicon sponge material, easy with the urethane foam production method of silicone resin modification, cost is low, and can make the shape of requirement earlier, handles with silicone resin again, can produce the product of various complicated shapes.
Describe the present invention below with reference to embodiment, should understand these embodiment and only be used for explanation, do not constitute limitation of the scope of the invention.
Embodiment
Embodiment 1
Commercially available volume density is 0.033g/cm
3Polyetber polyurethane foam, cut into 1000 * 1000 * 10 millimeters sheet materials.
The prescription of organosilicon resin composition is as follows:
107 RTV silicone resin, 100 weight parts
Gas-phase silica 20 weight parts
Titanium dioxide 5.8 weight parts
Phthalocyanine blue 0.2 weight part
Tetraethoxy 8 weight parts
Dibutyl tin laurate 4 weight parts
Add up to 138 weight parts
The organosilicon resin composition performance index are as follows:
| Before the curing | After the curing | ||
| Viscosity (25 ℃) | 25±5×10 4mPa·s | Tensile strength | 2.5Mpa |
| Proportion | 1.28g/cm 3 | Elongation | 110％ |
| Color | Blue | Tear strength | 3.5N/mm |
| Heat resisting temperature: 180-200 ℃ | |||
Adopt the print roll coating method, dip-coating organosilicon resin composition on urethane foam.Regulate roll gap and control glue spread, thus the silicone resin content and the heat resisting temperature of the urethane foam of making.Urethane foam sheet material after the coating continuously by several to up-down rollers, on roller, exert pressure, make the organosilicon resin composition infiltration sheet material internal layer of coating, make heat-resisting urethane foam in self-vulcanizing.
The volume density of the urethane foam that makes among this embodiment is 0.15g/cm
3, silicone resin content is 75%, heat resisting temperature is 180 ℃.
Substantially measure the distortion of the porous plastics that makes according to the described method of GB 7759-1996.160 ℃, after rate of compression was 70% time 72 hours, deformation values was 0.
This sheet material can use repeatedly as the bedding and padding of making up plant's whole ironing equipment.
Embodiment 2
Make heat-resisting foamed polyurethane plastics according to rank and embodiment 1 identical method.Difference is that the change of organosilicon resin composition prescription is as follows.
The prescription of organosilicon resin composition:
107 RTV silicone resin, 100 weight parts
Gas-phase silica 10 weight parts
Titanium dioxide 6 weight parts
Phthalocyanine blue 0.2 weight part
Tetraethoxy 6 weight parts
Dibutyl tin laurate 2 weight parts
Add up to 128.2 weight parts
The volume density of the urethane foam that makes is 0.15g/cm
3, silicone resin content is 75%, heat resisting temperature is 180 ℃.
Substantially measure the distortion of the porous plastics that makes according to the described method of GB 7759-1996.160 ℃, after rate of compression was 70% time 72 hours, deformation values was 0.
Embodiment 3
Commercially available volume density is 0.04g/cm
3Polyester urethtme foam, cut into 1000 * 1000 * 8 millimeters.
The prescription of organosilicon resin composition is as follows:
Elastosil LR 3003/40 A 100 weight parts
Barium sulfate 20 weight parts
Titanium dioxide 8 weight parts
Phthalocyanine blue 0.4 weight part
Elastosil LR 3003/40 B 100 weight parts
Silicone oil 60 weight parts
Add up to 296.4 weight parts
The organosilicon resin composition performance index are as follows:
| Before the curing | After the curing | ||
| Viscosity (25 ℃) | 8.5×10 5mPa·s | Tensile strength | 9.5Mpa |
| Proportion | 1.12g/cm 3 | Elongation | 620％ |
| Color | Blue | Tear strength | 26N/mm |
| Heat resisting temperature: 220 ℃ | |||
Make heat-resisting foamed polyurethane plastics according to the step identical with embodiment 1, difference is to use the scraper coating method.
Among this embodiment, silicone resin is the LR 3003/40 Elastosil LR 3003 resin series of buying from German Wacker company, divides two parts of A and B, A is a resin, B is catalyzer and solidifying agent, when the organosilicon resin composition of usefulness is flooded in preparation, A and B is mixed with other component.Flooded the urethane foam behind the organosilicon resin composition, in 170 ℃ hot blast drying tunnel, solidified 30 seconds.The volume density of the urethane foam that makes is 0.27g/cm
3, silicone resin content is 87%, heat resisting temperature is about 200 ℃.
Substantially measure the distortion of this porous plastics according to the described method of GB 7759-1996.170 ℃, after rate of compression was 50% time 72 hours, deformation values was 0.
Embodiment 4
Getting volume density is 0.040g/cm
3Polyester urethtme foam, cut into 1000 * 1000 * 20 millimeters.
The prescription of organosilicon resin composition is as follows:
GM silicone resin (RTV) 100 weight parts
Upright powder 10 weight parts
Red iron oxide 6 weight parts
Silicone oil 6 weight parts
Tetraethoxy 8 weight parts
Dibutyl tin laurate 4 weight parts
Add up to 132 weight parts
The organosilicon resin composition performance index are as follows:
| Before the curing | After the curing | ||
| Viscosity (25 ℃) | 40×10 4mPa·s | Tensile strength | 3.8Mpa |
| Proportion | 1.4g/cm 3 | Elongation | 100％ |
| Color | Red | Tear strength | 3.5N/mm |
| Heat resisting temperature: 200-230 ℃ | |||
Make heat-resisting foamed polyurethane plastics according to the step identical with embodiment 1.The urethane foam that makes, its volume density are 0.50g/cm
3, silicone resin content is 90%, heat resisting temperature is about 220 ℃.
Substantially measure the distortion of this porous plastics according to the described method of GB 7759-1996.Under 180 ℃, after rate of compression was 30% time 72 hours, deformation values was 0.
Embodiment 5
According to substantially identical method, make anti-high urethane foam with embodiment 4.Difference organosilicon resin composition prescription changes as follows.
The prescription of organosilicon resin composition is as follows:
GM silicone resin (RTV) 100 weight parts
Upright powder 10 weight parts
Red iron oxide 10 weight parts
Silicone oil 10 weight parts
Tetraethoxy 10 weight parts
Dibutyl tin laurate 6 weight parts
Add up to 146 weight parts
The urethane foam that makes, its volume density are 0.49g/cm
3, silicone resin content is 88%, heat resisting temperature is about 210 ℃.
Substantially measure the distortion of this porous plastics according to the described method of GB 7759-1996.Under 180 ℃, after rate of compression was 30% time 72 hours, deformation values was 0.
Embodiment 6
Getting volume density is 0.030g/cm
3Polyetber polyurethane foam, cut into 500 * 1000 * 4 millimeters sheet material.
The prescription of organosilicon resin composition is as follows:
107 RTV silicone resin, 100 weight parts
Gas-phase silica 5 weight parts
Aluminium hydroxide 20 weight parts
Decabromodiphynly oxide 8 weight parts
Sb
2O
35 weight parts
3ZnO2B
2O
32 weight parts
Tetraethoxy 6 weight parts
Dibutyl tin laurate 2 weight parts
Thinner 100 weight parts
Add up to 248 weight parts
The performance index of organosilicon resin composition are as follows:
| Before the curing | After the curing | ||
| Viscosity (25 ℃) | 40×10 4mPa·s | Tensile strength | ＞3.5Mpa |
| Proportion | 1.2g/cm 3 | Elongation | 200％ |
| Color | Grey | Tear strength | 35N/mm |
| Flame retardant grade: V (0) level | |||
Adopt spraying method, on urethane foam, be coated with silicone resin.Urethane foam sheet material after the coating continuously by several to up-down rollers, on roller, exert pressure, make the organosilicon resin composition infiltration sheet material internal layer of coating, make heat-resisting urethane foam in self-vulcanizing.
The urethane foam that makes, its volume density are 0.06g/cm
3, silicone resin and flame retardant agent content are 50%.
Measure the flame retardant resistance of this porous plastics according to U.S. UL 94 described methods.The fire-retardant rank of measuring is V (0).
Embodiment 7
Substantially make the urethane foam of anti-high flame retardant according to the method identical with embodiment 6.Difference is that the change of organosilicon resin composition prescription is as follows.
The prescription of organosilicon resin composition:
107 RTV silicone resin, 100 weight parts
Gas-phase silica 15 weight parts
Aluminium hydroxide 20 weight parts
Decabromodiphynly oxide 10 weight parts
Sb
2O
36 weight parts
3ZnO2B
2O
34 weight parts
Tetraethoxy 8 weight parts
Dibutyl tin laurate 4 weight parts
Thinner 80 weight parts
Add up to 247 weight parts
The urethane foam that makes, its volume density are 0.05g/cm
3, silicone resin and flame retardant agent content are 50%.
Measure the flame retardant resistance of this porous plastics according to U.S. UL 94 described methods.The fire-retardant rank of measuring is V (0).
Claims (7)
1. heat-resisting foamed polyurethane plastics, it is characterized in that described high temperature resistant porous plastics is to adopt print roll coating, scraper coating or spraying method to be coated with organosilicon resin composition on urethane foam, curing makes then, and the silicone resin content of the heat-resisting foamed polyurethane plastics that makes is 75-90% weight.
2. heat-resisting foamed polyurethane plastics as claimed in claim 1, the heat resisting temperature scope that it is characterized in that described heat-resisting foamed polyurethane plastics is 180-220 ℃, volume density is the 0.15-0.50 grams per cubic centimter.
3. heat-resisting foamed polyurethane plastics as claimed in claim 1, it is characterized in that described organosilicon resin composition comprise 100 weight part silicone resins, 2-6 weight part as the dibutyl tin laurate of catalyzer, solidifying agent, 10-20 weight part that the 4-10 weight part is selected from tetraethoxy and amine be selected from the toughener of gas-phase silica, barium sulfate and Li De powder, tinting material, the 0-100 weight part that the 0-10 weight part is selected from titanium dioxide, phthalocyanine blue and red iron oxide is selected from silicone oil and alkane oil thinning agent.
4. heat-resisting foamed polyurethane plastics as claimed in claim 3 is characterized in that it is liquid room temperature curing type silicone resin or heat-curing type silicone resin that described silicone resin is selected under the room temperature.
5. heat-resisting foamed polyurethane plastics as claimed in claim 3 is characterized in that described organosilicon resin composition comprises that also the 15-20 weight part is selected from the fire retardant of weisspiessglanz, decabromodiphynly oxide and zinc borate.
6. heat-resisting foamed polyurethane plastics as claimed in claim 1 is characterized in that described urethane foam is open cell type polyetber polyurethane foam or polyester urethtme foam.
7. heat-resisting foamed polyurethane plastics as claimed in claim 1 is as the bedding and padding of making up plant's whole ironing equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001370537A CN1140584C (en) | 2000-12-28 | 2000-12-28 | Heat-resisting foamed polyurethane plastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001370537A CN1140584C (en) | 2000-12-28 | 2000-12-28 | Heat-resisting foamed polyurethane plastics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1361221A CN1361221A (en) | 2002-07-31 |
| CN1140584C true CN1140584C (en) | 2004-03-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001370537A Expired - Fee Related CN1140584C (en) | 2000-12-28 | 2000-12-28 | Heat-resisting foamed polyurethane plastics |
Country Status (1)
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| CN (1) | CN1140584C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105742B (en) * | 2018-02-01 | 2021-12-21 | 中国石油化工股份有限公司 | Polyurethane foam material with skin-core structure, preparation method and sealing material thereof |
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| CN1361221A (en) | 2002-07-31 |
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Owner name: SHANGHAI QIANGCHEN RUBBER AND PLASTIC PRODUCTS CO Free format text: FORMER OWNER: SHANGHAI YINGQIANG RUBBER AND PLASTIC PRODUCT CO., LTD. Effective date: 20050930 |
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Effective date of registration: 20050930 Address after: 200434, 1200 Jiang Lu Road, Shanghai Patentee after: Shanghai strong rubber products Co., Ltd. Address before: 200433 No. 1059, Lane 4, Xiang Yin Road, Shanghai Patentee before: Shanghai Yingqiang Rubber and Plastic Product Co., Ltd. |
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