CN102061055B - Halogen-free flame-retardant resin composition and thermoplastic elastomer prepared from same - Google Patents
Halogen-free flame-retardant resin composition and thermoplastic elastomer prepared from same Download PDFInfo
- Publication number
- CN102061055B CN102061055B CN201010588354A CN201010588354A CN102061055B CN 102061055 B CN102061055 B CN 102061055B CN 201010588354 A CN201010588354 A CN 201010588354A CN 201010588354 A CN201010588354 A CN 201010588354A CN 102061055 B CN102061055 B CN 102061055B
- Authority
- CN
- China
- Prior art keywords
- propylene
- halogen
- ethylene copolymers
- ethylene
- sebs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a halogen-free flame-retardant composition and a thermoplastic elastomer prepared from the same. The halogen-free flame-retardant composition consists of the following raw materials in part by weight: 20 to 40 parts of styrene-ethylene-butadiene-styrene block copolymer (SEBS), 15 to 35 parts of propylene-ethylene copolymer, 5 to 20 parts of polypropylene, 5 to 20 parts of softening oil, 15 to 35 parts of phosphorus-nitrogen composite flame retardant and 1 to 5 parts of silicone powder, wherein the ethylene content of the propylene-ethylene copolymer is 8 to 16 percent. In the thermoplastic elastomer prepared from the halogen-free flame-retardant composition, the elongation rate exceeds 400 percent, the tensile strength is more than 12MPa, the hardness is not more than 80A, and the flame-retardant performance reaches UL94V0 standard; and the thermoplastic elastomer does not contain halogen, and is suitable for producing various electronic wires, plugs and the like with high flame-retardant requirement.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of fire-proof resin composition of halogen and by its flame-proof elastomer of processing.
Background technology
The modern life has the powerful demand of continuing to electronics or electrical equipment with wire rod.For this type material, people always expect that it has high tensile, high elongation at break, alap hardness, has high flame retardant resistance simultaneously.
Hydrogenated styrene-butadiene-styrene block copolymers (SEBS) is to be got through hydrogenation hydrogenation by thermoplastic elastomer SBS's (styrene-butadiene-styrene block copolymer).Carbon-to-carbon double bond is by saturated in its molecular structure, thereby has performances such as good weather-proof, anti-aging, heat-resisting, compression, and use temperature is up to 130 ℃.Especially valuable is, and it has recyclable even with, product properties again, size accurate advantages such as control easily, thereby is widely used in fields such as electrical equipment, cable.But SEBS and intermingling material goods thereof are inflammable, therefore are that the fire-retardant problem of matrix material on basis has caused concern widely with SEBS.Early stage halide-containing is used widely in the electric wire industry owing to having good flame retardant property, but not only emits a large amount of smog after the burning, and can discharge poisonous corrosive hydrogen halides gas, conflicts with safety and environmental protection theory in recent years.Therefore, it is significant SEBS to be that the matrix material of main body carries out halogen-free flameproof research.
CN101469100A has described with preparation flame-proof elastomers such as SEBS, white oil, coated ammonium polyphosphate, macro molecular triazine verivate, organic Halogen phosphorus flame retardants; Can reach the UL-94V-0 grade standard; But the tensile strength of this material is not ideal enough, only between 6-8MPa.CN100436536C has described the flame retardant rubber with preparations such as SEBS, softening oil, nano-inorganic substance, nitrogen-phosphorus composite flame-retardant agents, and the flame retardant effect of this prescription in order to obtain to expect introduced a large amount of nitrogen-phosphorus series composite flame retardant, and the result makes the hardness of product higher.For with Hardness Control between 70-90A, will fill softening oil usually, but the existence of softening oil can influence flame retardant effect conversely unfriendly.In addition, the increase of fire retardant consumption also causes physicals declines such as polymer strength, increases cost simultaneously.
Patent of invention CN101157789A has described with a kind of non-bittern flame-proof elastomer composite materials of preparation such as Ethylene-Propylene Block Copolymer, SEBS, Injecatable EVA Copolymer (EVA), Marinco H, encapsulated red phosphorus; Its product tensile strength is greater than 12MPa; Elongation is greater than 300%, and fire-retardant rank reaches the UL94V-0 level.Though this patent avoids the use of softening oil, regulate material hardness through Ethylene-Propylene Block Copolymer, do fire retardant, make synergist with Marinco H with red phosphorus.Make fire retardant with Marinco H, flame retarding efficiency is low, and is poor with the resin body consistency, and loading level is big in the time of reaching certain flame retardant effect, is prone to cause that material mechanical performance (like tensile strength, elongation etc.) is serious descends and the hardness rising; And the red phosphorus moisture absorption is made moist, be prone to oxidation, and is poor with resin compatible, the long-term phosphine gas that can emit severe toxicity that contacts with air, and contaminate environment, exsiccant red phosphorus dust has the danger of blast.
Summary of the invention
Therefore the present invention proposes a kind of new fire-proof resin composition, to overcome the defective that existing fire retardant material can not obtain desired tensile strength, elongation at break, flame retardant resistance and hardness simultaneously.
Halogen-free fire-proof resin composition of the present invention mainly is made up of following weight part raw material:
SEBS 20-40 part,
Propylene-ethylene copolymers 15-35 part,
Vestolen PP 7052 5-20 part,
Softening oil 5-20 part,
Phosphorus-nitrogen composite fire retardant 15-35 part,
Silicone powder 1-5 part,
Wherein, the ethylene content in the propylene-ethylene copolymers is 8-16%.
In a kind of preferred implementation, this halogen-free fire-proof resin composition mainly is made up of following weight part raw material:
SEBS 25-35 part,
Propylene-ethylene copolymers 20-30 part,
Vestolen PP 7052 5-10 part,
Softening oil 5-10 part,
Phosphorus-nitrogen composite fire retardant 20-30 part,
Silicone powder 1-5 part,
Wherein, the ethylene content in the propylene-ethylene copolymers is 10-15%.
The invention still further relates to the Halogen thermoplastic elastic material of being processed by above-mentioned compsn, it is extruded and gets with forcing machine after each feed composition is mixed, and the preparation method is simple unusually.
The flame retardant resistance that the halogen thermoplastic elastic material that makes according to the present invention can reach tensile strength greater than 12MPa, the elongation at break greater than 400% simultaneously, not be higher than the hardness of 80A and reach the UL94V0 level.
Embodiment
Halogen-free fire-proof resin composition of the present invention mainly is made up of following raw material by weight: SEBS 20-40 part; Propylene-ethylene copolymers 15-35 part, Vestolen PP 7052 5-20 part, softening oil 5-20 part; Phosphorus-nitrogen composite fire retardant 15-35 part; Silicone powder 1-5 part, wherein, the ethylene content in the propylene-ethylene copolymers is 8-16%.
In fire-proof resin composition of the present invention, propylene-ethylene copolymers, Vestolen PP 7052 and SEBS is composite, as the matrix of resin material, and the introducing ratio of strict control fire retardant, avoid reducing the mechanical property of resin material because of the introducing of fire retardants in a large number.Wherein, the molecular weight of the propylene-ethylene copolymers that the present invention adopted is in the 150000-250000 scope, and polyacrylic molecular weight is in the 200000-300000 scope, and the molecular weight of SEBS is in the 100000-200000 scope.
Another characteristics of the present invention are, the content of ethene in the propylene-ethylene copolymers are controlled between the 8-16%, preferably between 10-15.If ethylene content is lower than 8%, then hardness is too big, causes resin combination hardness higher; If ethylene content is higher than 16%, then tensile strength and softening temperature can reduce, and influence the whole rerum natura of resin.Through between 8-16%, regulating ethylene content, the hardness of may command Ethylene-Propylene Block Copolymer and mechanical property, thus can regulate elastomeric hardness, reduce the addition of softening oil, finally reach the purpose that elastomerics flame retardant resistance and mechanical property balance each other.
The present invention has introduced an amount of silicone powder, and itself and above-mentioned resin matrix have good consistency, has played to promote fire-retardant effect, can improve the surface property of Drawing abillity and goods simultaneously, improves surface gloss, slickness and wear resistance.
Because it is composite that the present invention carries out above-mentioned mixed matrix, fire retardant and silicone powder with specified proportion, thereby under the prerequisite that obtains ideal elongation at break and tensile strength, reduced the use of softening oil.In the present invention, the consumption of softening oil is no more than 20% of composition weight, under preferred situation, can be no more than 10% of composition weight.
In a kind of preferred implementation, propylene-ethylene copolymers is the semi-crystalline co-polymers of propylene and ethene, and the effect of physical crosslinking point is played in crystallization in this polymkeric substance, thereby gives multipolymer certain elasticity under typical conditions.
Can be used for phosphorus of the present invention-nitrogen composite fire retardant has multiplely, and operable example comprises ammonium polyphosphate (APP), melamine phosphate (MP), Melamine Polyphosphate (MPP), 2,4,8; 10-four oxygen-3,9-hosphospiro [5,5] undecane-3; 9-dioxy-3,9-two melamine salts, two (2,6; 7-three oxygen-1-phosphorus-dicyclo [2,2,2] octane-1-oxygen methyl) phosphoric acid candy melamine salt (Melabis).A kind of screening formulation of the present invention is: SEBS 25-35 part, propylene-ethylene copolymers 20-30 part, Vestolen PP 7052 5-10 part; Softening oil 5-10 part, phosphorus-nitrogen composite fire retardant 20-30 part, silicone powder 1-5 part; Wherein, the ethylene content in the propylene-ethylene copolymers is 10-15%.
More than described the various staples of thing combined according to the invention, said composition can also be introduced a small amount of ancillary component, for example inhibitor (for example oxidation inhibitor 908), lubricant (for example, fatty acid metal soap class, calcium stearate etc.).
Do not use proportion mineral filler bigger than normal among the present invention, so gained elastomerics light specific gravity, rebound resilience and flexibility are good.
Another aspect of the present invention is to provide a kind of Halogen thermoplastic elastomer that is made by above-mentioned fire-retardant combination, after above-mentioned compsn is mixed, extrudes with forcing machine and can make above-mentioned elastomerics.
The method for preparing flame-proof elastomer composite material of the present invention is very simple, after only needing various compositions are put into high-speed mixer and mix, with twin screw extruder extrude, granulation all can, extruder temperature is 180-200 ℃, screw speed is 200400rpm.
Embodiment 1-5
According to the prescription in the table 1, after all components mixed, again through twin screw extruder extrude, granulation, wherein,
Ethylene-propylene copolymer: Vistamaxx 6202, Exxonmobil;
Vestolen PP 7052: 3342, Thailand's petrochemical industry;
Fire retardant: Melamine Polyphosphate, MPP, Zhenjiang star fire retardant ltd;
Silicone powder: TCP-5012, Guangzhou Tianci Organic Silicon Science and Technology Co., Ltd;
Softening oil: KN4006, the Kelamayi petrochemical industry.
The proportioning raw materials of table 1 embodiment 1-5
The granular resin that embodiment 1-5 is made is injection molded into sheet in injection moulding machine, measure its physicals and combustionproperty, sees table 2.
The measure of merit data of each embodiment of table 2
The description of above specific embodiments of the invention and embodiment is to be used for explanation and purpose of description, should not regard limitation of the present invention as.They are not detailed or limit the invention to the precise forms that disclosed, and obviously according to above-mentioned instruction, many improvement, embodiment and to change be possible.Therefore, scope of the present invention comprises field as this paper discloses, and by accompanying claims with and equivalence replacement contained.
Claims (7)
1. a flame retardant resin composition without halogen mainly is made up of following weight part raw material: SEBS 20-40 part, propylene-ethylene copolymers 15-35 part; Vestolen PP 7052 5-20 part, softening oil 5-20 part, phosphorus-nitrogen composite fire retardant 15-35 part; Silicone powder 1-5 part, wherein, the ethylene content in the propylene-ethylene copolymers is 8-16%; Wherein, The molecular weight of said propylene-ethylene copolymers is in the 150000-250000 scope, and said polyacrylic molecular weight is in the 200000-300000 scope, and the molecular weight of said SEBS is in the 100000-200000 scope.
2. flame retardant resin composition without halogen according to claim 1, wherein, said propylene-ethylene copolymers is the semi-crystalline co-polymers of propylene and ethene.
3. flame retardant resin composition without halogen according to claim 1, wherein, said phosphorus-nitrogen composite fire retardant is ammonium polyphosphate or Melamine Polyphosphate.
4. flame retardant resin composition without halogen according to claim 1 mainly is made up of following weight part raw material: SEBS 25-35 part, propylene-ethylene copolymers 20-30 part; Vestolen PP 7052 5-10 part; Softening oil 5-10 part, phosphorus-nitrogen composite fire retardant 20-30 part, silicone powder 1-5 part; Wherein, the ethylene content in the propylene-ethylene copolymers is 10-15%.
5. a halogen-free thermoplastic elastomerics is mainly processed by following weight part raw material: SEBS 20-40 part, propylene-ethylene copolymers 15-35 part; Vestolen PP 7052 5-20 part, softening oil 5-20 part, phosphorus-nitrogen composite fire retardant 15-35 part; Silicone powder 1-5 part, wherein, the ethylene content in the propylene-ethylene copolymers is 8-16%; Wherein, The molecular weight of said propylene-ethylene copolymers is in the 150000-250000 scope, and said polyacrylic molecular weight is in the 200000-300000 scope, and the molecular weight of said SEBS is in the 100000-200000 scope.
6. halogen-free thermoplastic elastomerics according to claim 5 mainly is made up of following weight part raw material: SEBS25-35 part, propylene-ethylene copolymers 20-30 part; Vestolen PP 7052 5-10 part; Softening oil 5-10 part, phosphorus-nitrogen composite fire retardant 20-30 part, silicone powder 1-5 part; Wherein, the ethylene content in the propylene-ethylene copolymers is 10-15%.
7. halogen-free thermoplastic elastomerics according to claim 5 is characterized in that, said elastomerics is through after each feed composition is mixed, and extrudes with forcing machine to be prepared from.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010588354A CN102061055B (en) | 2010-12-14 | 2010-12-14 | Halogen-free flame-retardant resin composition and thermoplastic elastomer prepared from same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010588354A CN102061055B (en) | 2010-12-14 | 2010-12-14 | Halogen-free flame-retardant resin composition and thermoplastic elastomer prepared from same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102061055A CN102061055A (en) | 2011-05-18 |
| CN102061055B true CN102061055B (en) | 2012-08-29 |
Family
ID=43996567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010588354A Expired - Fee Related CN102061055B (en) | 2010-12-14 | 2010-12-14 | Halogen-free flame-retardant resin composition and thermoplastic elastomer prepared from same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102061055B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897324A (en) * | 2012-12-27 | 2014-07-02 | 中纺投资发展股份有限公司 | Halogen-free flame-retardant polyphenyl ether composition and preparation method thereof |
| CN104403252A (en) * | 2014-11-17 | 2015-03-11 | 宁波市青湖弹性体科技有限公司 | Flexible halogen-free and flame-retardant TPE (thermoplastic elastomer) with low smoke density and preparation method of TPE |
| CN104559022A (en) * | 2014-12-31 | 2015-04-29 | 上海俊尓新材料有限公司 | Thermoplastic elastomer composition and preparation method thereof |
| CN106009283A (en) * | 2016-06-30 | 2016-10-12 | 台州携康电子有限公司 | Plug |
| CN110527315A (en) * | 2018-05-23 | 2019-12-03 | 天津泰煜辉新材料科技有限公司 | A kind of high-elasticity halogen-free flame-resistant thermoplastic elastomer and preparation method thereof |
| CN109679270A (en) * | 2018-11-21 | 2019-04-26 | 苏州市同发塑业有限公司 | A kind of ABS composite material and preparation method thereof of fire-retardant dumb light |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884367A (en) * | 2006-06-04 | 2006-12-27 | 浙江三博聚合物有限公司 | Expansion type low-smoke halogen-free thermoplastic flame-retardant rubber and its production method |
| CN101157789A (en) * | 2007-09-30 | 2008-04-09 | 上海金发科技发展有限公司 | Non-bittern flame-proof elastomer composite material and method for making same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL2176347T3 (en) * | 2007-07-17 | 2011-06-30 | Styron Europe Gmbh | Compositions exhibiting high escr and comprising monovinylidene aromatic polymer and ethylene/alpha-olefin copolymer |
-
2010
- 2010-12-14 CN CN201010588354A patent/CN102061055B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884367A (en) * | 2006-06-04 | 2006-12-27 | 浙江三博聚合物有限公司 | Expansion type low-smoke halogen-free thermoplastic flame-retardant rubber and its production method |
| CN101157789A (en) * | 2007-09-30 | 2008-04-09 | 上海金发科技发展有限公司 | Non-bittern flame-proof elastomer composite material and method for making same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102061055A (en) | 2011-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102061055B (en) | Halogen-free flame-retardant resin composition and thermoplastic elastomer prepared from same | |
| CA2771074C (en) | Thermoplastic elastomer compositions comprising intumescent flame retardants and non-phosphorous-based flame retardant synergists | |
| CN101597409B (en) | Expanding type halogen-free flame retarding thermoplastic dynamic vulcanizate composition | |
| CA2778120C (en) | Thermoplastic polyurethane composition with high insulation resistance | |
| CN102947387B (en) | The composition of the styrene-based based block copolymer of flame-retardant nature with enhancing | |
| CA2763300C (en) | Thermoplastic composition with epoxidized novolac | |
| CA2769007A1 (en) | Flame retardant thermoplastic elastomer | |
| KR20120120932A (en) | Thermoplastic polymer blends comprising crosslinked polar olefin polymers in a thermoplastic polyurethane matrix | |
| CN103910990A (en) | Thermoplastic halogen-free flame-retardant polyphenyl ether elastomer cable material and preparation method thereof | |
| CN105860412A (en) | Halogen-free flame-retardant thermoplastic elastomer material for electric wires and cables and preparation method of material | |
| CN104403227A (en) | Silica gel-like flame-retardant polyvinyl chloride plastic | |
| CN102634105A (en) | Soft halogen-free flame-retardant cable material | |
| CN104356538A (en) | Flame-retardant smoke-eliminating polyvinyl chloride wire and cable material | |
| CN101157789B (en) | Non-bittern flame-proof elastomer composite material and method for making same | |
| CA2794905C (en) | Flame-retardant thermoplastic elastomer composition with resistance to scratch-whitening | |
| KR20020077579A (en) | Polypropylene resin composition for nondripping extensible fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 413000, Hunan, Yiyang City, Fu Fu South Road, Ring Road South (City Civil Air Defense Office opposite) Patentee after: Yiyang Sunstar Technologies Co., Ltd. Address before: 413000, 1, Zi Shan Road, Yiyang, Hunan (High-tech Zone Economic and Trade Bureau) Patentee before: Yiyang Sunstar Technologies Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20180411 Address after: 518118 Pingshan office six, Pingshan street, Pingshan District, Shenzhen, Guangdong, and fourth buildings first, 1, 2 and 4, 1-4 buildings, first 1-4 floors of the community's high st industrial area. Patentee after: Sata Austria (Shenzhen) Co., Ltd. elastomer Address before: 413000, Hunan, Yiyang City, Fu Fu South Road, Ring Road South (City Civil Air Defense Office opposite) Patentee before: Yiyang Sunstar Technologies Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120829 Termination date: 20191214 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |