CN102286157B - Fluoropolymer processing aid, silane cross-linked polyethylene composition containing fluoropolymer processing aid and application of fluoropolymer processing aid - Google Patents
Fluoropolymer processing aid, silane cross-linked polyethylene composition containing fluoropolymer processing aid and application of fluoropolymer processing aid Download PDFInfo
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- CN102286157B CN102286157B CN 201110165285 CN201110165285A CN102286157B CN 102286157 B CN102286157 B CN 102286157B CN 201110165285 CN201110165285 CN 201110165285 CN 201110165285 A CN201110165285 A CN 201110165285A CN 102286157 B CN102286157 B CN 102286157B
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Abstract
The invention provides a fluoropolymer processing aid. The fluoropolymer processing aid is particles which are formed by a core part and a shell part and have average particle diameter of 0.2 to 1 micron, wherein the core part is made of fluorocarbon polymer, the shell part is made of MQ silicon resin, the ratio of M to Q is 0.5 to 0.9, and the weight ratio of the core part to the shell part is 20:80-45:55. The invention also provides a silane cross-linked polyethylene composition containing the processing aid and application of the fluoropolymer processing aid in silane cross-linked polyethylene extrusion molding. Not only the silane cross-linked polyethylene added with the fluoropolymer processing aid has high extrusion velocity, but also the extruded product has high surface finishment.
Description
Technical field
The present invention relates to fluoropolymer additive, contain its organosilane crosslinked polyethylene and application thereof, particularly relate to fluoropolymer additive, the organosilane crosslinked polyethylene that contains it and the application thereof of silicone resin improvement.
Background technology
There is critical shearing rate in polymkeric substance in extrusion process, under critical shear rate, and the smooth surface of extrudate, and surpassed critical shear rate, the extrudate surface is because melt fracture can become coarse.Melt fracture different states can occur with the rising of shearing rate.When the shearing rate of extruding is higher than critical shear rate, equipment mouth die wall increases the resistance of melt, cause the melt flow rate at edge less, the stress that the elastic recoil that a large amount of elastic energy of storage produces in mouth mould exit in the melt causes has been torn melt, forms so-called shark skin.The degree of melt fracture can increase along with the increase of shearing rate.When shearing rate high during to certain value more than critical shear rate, the melt at mouthful die wall place can stick and slides between swing, form the melt fracture that circulates.
Residual micro-moisture all in organosilane crosslinked polyethylene and the catalyst masterbatch, also can introduce moisture in the two mixing and the extrusion in addition, so that organosilane cross-linked poly-ethylene cable material easily hydrolysis-condensation reaction occurs and produces precrosslink in storage and extrusion process.The precrosslink reaction makes the molecule quantitative change of organosilane crosslinked polyethylene large, and viscosity increases, and extrudes poor processability, and severe patient can make cable insulation produce defective, and air spots is sliding.Under many circumstances, this phenomenon can cause spark fault or electrical breakdown.
Therefore, need a kind of processing aid in this area, to suppress the precrosslink reaction in the organosilane crosslinked polyethylene, improve the processing characteristics of organosilane crosslinked polyethylene, prevent the mass defect that causes owing to precrosslink and the electric breakdown phenomena that may in cable application, cause.
Summary of the invention
The purpose of this invention is to provide a kind of multi-functional fluoropolymer additive.This processing aid is extruded for silane cross-linked polyolefin and is added man-hour, can significantly improve extruded velocity and improve surface smoothness.Acidic-group part in this polymkeric substance can suppress the precrosslink of organosilane crosslinked polyethylene in extrusion, has avoided because the mass defect that precrosslink causes and the electric breakdown phenomena that may cause in cable application.
Fluoropolymer additive of the present invention, the median size that is formed by core and shell section is the micropartical of 0.2～1 μ m, described core is made of fluorocarbon polymer, and described shell section is made of silicone resin, and the weight ratio of described core and shell section is 20: 80～45: 55.
The preparation method of fluoropolymer additive of the present invention is included in in-situ hydrolysis closure agent and silicate monomer mixture under the existence of fluorocarbon polymer corpuscle emulsion.
The present invention also provides a kind of polyethylene composition of crosslinked with silicane, and it contains 1000 weight part organosilane crosslinked polyethylenes and the above-mentioned fluoropolymer additive of 0.1～5 weight part.
The present invention also provides the application of above-mentioned fluoropolymer additive in the organosilane crosslinked polyethylene extrusion moulding.
Embodiment
In fluoropolymer additive of the present invention, the fluorocarbon polymer core material generally is the homopolymer of unsaturated fluorochemical monomer or the multipolymer of various of monomer.Fluorochemical monomer comprises Fluorine containing olefine homopolymer or the multipolymers such as a chlorotrifluoroethylene, vinylidene, R 1216, tetrafluoroethylene, fluoroalkyl ethene, fluoroalkyl fluorovinyl ether, fluoropolymers such as tetrafluoroethylene, R 1216-TFE copolymer F46, vinylidene fluoride-hexafluoropropylene copolymer F26, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, ethylene-tetrafluoroethylene copolymer F40, tetrafluoroethylene-vinyl ether co-polymer, ethylene-tetrafluoroethylene-vinyl ether co-polymer.
This fluorocarbon polymer core material generally makes by the free-radical emulsion polymerization method, and the median size of fluorocarbon polymer particle is generally the 0.1-0.4 micron, is preferably the 0.15-0.25 micron.The weight-average molecular weight of this fluorocarbon polymer is generally 10-1000 ten thousand, is preferably 50-500 ten thousand.
In a preferred embodiment of the present invention, this fluorocarbon polymer core material is hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, vinylidene-hexafluoroethylene multipolymer and their mixture.
Above-mentioned fluorocarbon polymer comprises vinylidene-hexafluoroethylene multipolymer more preferably in the embodiment at one of the present invention, and the weight-average molecular weight of this fluorocarbon polymer is 500,000-5,000,000.
We find in experiment, if hydrolysis closure agent and organosilicon acid esters monomer or its mixture under the existence of above-mentioned fluorocarbon polymer core corpuscle emulsion, can form the hard monomer polymeric coating at the fluorocarbon polymer microparticle surfaces, originally soft amorphous carbon fluoropolymer is coated on polysiloxane coating (particularly MQ silicone resin) the inside, thereby improved the surface property of fluorocarbon polymer particulate, and improved the dispersiveness of fluorocarbon polymer particulate in organosilane crosslinked polyethylene.
In fluoropolymer additive of the present invention, above-mentioned MQ silicone resin refers to contain M chain link (R
3SiO
0.5) and Q chain link (SiO
2) polysiloxane, R is preferably H in the formula, C
1-4Alkyl such as methyl or ethyl, C
2-4Thiazolinyl such as vinyl or propenyl, or C
6-10Aryl such as phenyl.It is polymerized by closure agent and silicate monomer.Wherein, silicate monomer is tetraethoxy, methyl silicate, oligomeric tetraethoxy, oligomeric methyl silicate or its mixture.Closure agent is divinyl tetramethyl disiloxane, hexamethyldisiloxane or its mixture.
The preparation method of above-mentioned MQ silicone resin at first will add closure agent and silicate monomer in reactor, strong acid example hydrochloric acid or sulfuric acid, deionized water, one or more mixtures such as solvent such as toluene, dimethylbenzene, butanone or ethanol.Then add while stirring the core emulsion solution, the condensation that is hydrolyzed kept the hydrolyzed state stirring reaction 1-10 hour, preferred 2-5 hour, reaction was carried out fully.Add at last the toluene extraction, extraction process 1～4 hour, pour reaction solution in separating funnel layering after preferred 1～2 hour, with the water layer subregion, oil-reservoir water is washed till neutrality, obtains fluoropolymer additive after the distillation drying is removed toluene, and drying makes water content less than 5%, preferably less than 1%, obtain the final polymer processing aid.
In order effectively to control the process of separating out with polymerization, guarantee the stable and size distribution of precipitation particles, the pH value of conditioned reaction liquid adds a small amount of tensio-active agent in advance, and adds the part separant after adding core polymer emulsion and shell section monomer mixture solution.The pH value of conditioned reaction liquid is 1-7, and preferred 2-6 can control the process of separating out with polymerization.The strong acid such as sulfuric acid, hydrochloric acid, nitric acid are preferred pH value conditioning agent and stablizer.Add tensio-active agent and can guarantee stablizing and size distribution of precipitation particles, negatively charged ion and the nonionogenic tensides such as polyoxyethylenated alcohol, fatty alcohol-polyoxyethylene ether, oxyethane propane multipolymer or fluorine-containing alkyl ether in sulfonate commonly used or alkyl benzene sulfonate, alkylphosphonic, alkylphenol polyoxyethylene, the mountain.Add separant and can avoid free monomer to be clamminess, stirring rake and kettle are damaged, and stable particle.The separant that uses in the building-up process can be inorganic or organic separants such as calcium carbonate, talcum powder, kaolin, calcium phosphate, calcium sulfate, barium sulfate, methylene blue, silicone oil, silicon powder, Mierocrystalline cellulose, pectin, guar gum, polyvinyl alcohol, poly-Sodium Propionate, and add-on is the 0.01-10% of reaction-ure mixture.
Form the preferred M/Q=0.5-1.0 of MQ silicone resin on micropartical surface with above-mentioned method for hydrolysis, more preferably 0.5～0.9.The median size of the fluoropolymer through coating that makes with aforesaid method is 0.2～1 μ m, is preferably 0.5～1 micron, more preferably 0.7～0.9 micron.The weight ratio of core and shell section is generally 20: 80～and 45: 55, be preferably 25: 75～40: 60.
It is the aggregate of 1 μ m～5mm that the further aggegation of the general meeting of these polymeric microspheres becomes particle diameter.
With the 0.1-5 weight part, preferred 0.3-2 weight part fluoropolymer additive of the present invention joins in the 1000 weight part organosilane crosslinked polyethylenes, use conventional single screw rod or twin screw extruder, Banbury mixer divides dispersing plasticizing to extrude or blown film again, injection moulding, or make first 1-20% master batch reprocessing moulding, form the goods such as pipe, conduit, wire coating or film.
Used organosilane crosslinked polyethylene for example comprises the organosilane crosslinked polyethylene that the Sioplas E two-step approach of developing by U.S. Dow corning company or the Monosil single stage method of developing by BICC and Nailefer company prepare among the present invention.One-step silane cross-linked polyethylene is for example referring to United States Patent (USP) 4117195, CN1198177A and CN1245187A.The two-step approach organosilane crosslinked polyethylene is for example referring to United States Patent (USP) 3646155, CN1195673 and EP0548565A1.The content of above-mentioned patent with referring to mode introduce among the application.
Not only extruded velocity is fast for the organosilane crosslinked polyethylene of adding fluoropolymer additive of the present invention, and the surface smoothness of extruded product is high.
Embodiment
The invention will be further described by the following examples, but these embodiment only are illustratives, and can not be used for limiting the scope of the invention.
Gel content % among the embodiment measures according to the described method of GB/T18474-2001.
The M/Q of silicone resin is than measuring by the thermogravimetic analysis (TGA) method, and the model of used thermal gravimetric analyzer is the Simultaneous of the anti-company of speeding of Germany.
Embodiment 1
With thermometer, add 6 gram hexamethyldisiloxane in the 250ml there-necked flask of reflux and whipping appts, 0.3ml concentrated hydrochloric acid, the mixed solution of 3ml deionized water and 6ml ethanol, then start stirring, then in 1 hour, drip the concentrated dispersion liquid (FKM emulsion L636,30% solid content is available from Solvay Solexis S.P.A) of the poly-FKM of 50 grams.Then splash into fast the hydrolyzing condensation of ethyl silicate of 15 grams, be hydrolyzed after 1 hour, add the extraction of 50ml toluene, pour reaction solution in separating funnel layering after 1 hour, with the water layer subregion, oil-reservoir water is washed till neutrality, distillation is dry removes solid 29.1 grams that obtain white powder behind the toluene and is white microballoon, median size is 0.5mm, and wherein fluorocarbon polymer content is 38 % by weight, and the M/Q ratio of the silicone resin that records is 0.59.
Embodiment 2
Manufacturing process changes silane monomer into 1,3 divinyl-1,1,3,3 ,-tetramethyl disiloxane and 12 tetraethoxys that restrain of 7.2 grams with embodiment 1.Reaction product obtains processing aid 27.5 grams through washing and drying, is white microballoon, and median size is 0.57mm, and wherein fluorocarbon polymer content is 40 % by weight, and the M/Q of the silicone resin that records is 0.73.
Embodiment 3
Manufacturing process changes silane monomer into 1,3 divinyl-1,1,3,3 ,-tetramethyl disiloxane and 11.2 methyl silicates that restrain of 8.3 grams with embodiment 1.Reaction product obtains processing aid 28.5 grams through washing and drying, is white microballoon, and median size is 0.73mm, and wherein fluorocarbon polymer content is 32 % by weight, and the M/Q of the silicone resin that records is 0.82.
Embodiment 4
Manufacturing process changes silane monomer into hexamethyldisiloxane and the methyl silicate of 10.2 grams and the tetraethoxy of 9.8 grams of 7.4 grams with embodiment 1.Reaction product obtains processing aid 35.3 grams through washing and drying, is white microballoon, and median size is 0.33mm, and wherein fluorocarbon polymer content is 27 % by weight, and the M/Q of the silicone resin that records is 0.55.
The performance test of fluoropolymer of the present invention
1. the preparation of specimen sample
4 embodiment of the present invention are added respectively in the one-step method silanes crosslinked material of Monosil with capillary rheology instrument mensuration flow state.Above-mentioned processing aid is made respectively 5% masterbatch with twin screw extruder (L/D40: 1, φ 20 dual-screw pelletizers, Shanghai Bo Lima mechanical equipment factory), and vector resin uses the LLDPE (Shandong 7042) of MI=2.The sample that contains the processing aid of testing content by above-mentioned masterbatch and one-step method silanes crosslinked material by forming than row mixing granulation.
2. the critical shear rate of melt fracture appears in the test 1-4 crosslinked with silicane material that relatively contains different processing aids with capillary rheometer
Use Rheofixer capillary rheometer (length-to-diameter ratio 40: 1, mouthful mould 1mm, 200 ℃ of temperature) to extrude batten observation by light microscope surface melt fracture in this test, testing standard is pressed ISO 11443-1995.Each clean with cleaning material before switching sample, then repeat out to continue again next sample behind the equifinality of sample 0 with the crosslinked material of pure silane.Testing data sees Table 1.
Table 1
| Test | Processing aid | Effective content % | Critical shear rate |
| 0 | 0 | 300s -1 | |
| 1 | Embodiment 1 | 0.05 | ＞1800s -1 |
| 2 | Embodiment 2 | 0.05 | ＞1800s -1 |
| 3 | Embodiment 3 | 0.05 | ＞1800s -1 |
| 4 | Embodiment 4 | 0.05 | ＞1800s -1 |
The crosslinked with silicane material that data presentation does not contain processing aid under above-mentioned test conditions at 300s
-1Shearing rate under melt fracture appears, add different processing aids after, critical shear rate increases.
3. test 5-13 assesses different processing aids to the restraining effect of precrosslink according to the gel content testing method of GBT 18474-2001.
Test materials uses the sample of aforesaid method preparation.Forcing machine uses 20: 1 single screw extrusion machine of length-to-diameter ratio, and port mould diameter 2mm. is at 200 ℃, 400s
-1Shearing rate under, extrude the prescription 7-19, steady extruding is after 10 minutes, the 5-13 that will fill a prescription takes a sample respectively, measures respectively the gel content of different ingredients after extruding according to the described method of GBT 18474-2001.
Table 2
| Test | Processing aid | Effective content % | Gel content % |
| 5 | 0 | 42 | |
| 6 | Embodiment 1 | 0.05 | 18 |
| 7 | Embodiment 1 | 0.10 | 13 |
| 8 | Embodiment 2 | 0.05 | 22 |
| 9 | Embodiment 2 | 0.10 | 16 |
| 10 | Embodiment 3 | 0.05 | 19 |
| 11 | Embodiment 3 | 0.10 | 11 |
| 12 | Embodiment 4 | 0.05 | 19 |
| 13 | Embodiment 4 | 0.10 | 14 |
Data presentation fluoropolymer itself does not have restraining effect to the precrosslink in the extrusion, and fluoropolymer process aid of the present invention has obvious restraining effect to the precrosslink phenomenon in extruding.
4. test 14-22 measures among the present invention fluoropolymer additive to the impact of rate of crosslinking and degree of crosslinking.
Test 5-13 used sample is carried out crosslinked in 95 ℃ hot water, survey the gel content under the different crosslinking times, data see Table in 3.
Table 3
By table 3 data presentation, add different fluoropolymer additives to rate of crosslinking and almost not impact of degree of crosslinking.
Claims (9)
1. fluoropolymer additive, it is to be the micropartical of 0.2～1 μ m by the median size that core and shell section form, described core is that 100,000-1,000 ten thousand fluorocarbon polymer consists of by weight-average molecular weight, described shell section is the MQ silicone resin of M/Q=0.5～0.9, and the weight ratio of described core and shell section is 20:80～45:55.
2. fluoropolymer additive as claimed in claim 1 is characterized in that described fluorocarbon polymer is selected from tetrafluoroethylene, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene fluoride copolymers, vinylidene fluoride-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene-vinyl ether co-polymer and their mixture.
3. fluoropolymer additive as claimed in claim 2 is characterized in that, described fluorocarbon polymer comprises vinylidene fluoride-hexafluoropropylene copolymer, and the weight-average molecular weight of this fluorocarbon polymer is 500,000-5,000,000.
4. fluoropolymer additive as claimed in claim 1 is characterized in that, the weight ratio of described core and shell section is 25:75～40:60, and it is the aggregate of 1 μ m～5mm that the further aggegation of described micropartical becomes particle diameter.
5. the preparation method of a fluoropolymer additive claimed in claim 1, it is included in in-situ hydrolysis closure agent and silicate monomer mixture under the existence of fluorocarbon polymer corpuscle emulsion.
6. the preparation method of fluoropolymer additive as claimed in claim 5, it is characterized in that, described closure agent is divinyl tetramethyl disiloxane, hexamethyldisiloxane or their mixture, and described silicate monomer is tetraethoxy, methyl silicate, oligomeric tetraethoxy, oligomeric methyl silicate or their mixture.
7. the polyethylene composition of a crosslinked with silicane, it comprises:
A) 1000 weight part organosilane crosslinked polyethylenes,
B) each described fluoropolymer additive among 0.1～5 weight part claim 1-4.
8. the polyethylene composition of crosslinked with silicane claimed in claim 7 is characterized in that the polyethylene of described crosslinked with silicane comprises the organosilane crosslinked polyethylene for preparing by Sioplas E two-step approach or Monosil single stage method.
9. each described fluoropolymer additive application in the organosilane crosslinked polyethylene extrusion moulding among the claim 1-4.
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| TWI492978B (en) * | 2013-07-24 | 2015-07-21 | Grand Tek Advance Material Science Co Ltd | Composite micropowder, ceramic paint, protective coating, and method for manufacturing composite micropowder |
| WO2018001028A1 (en) * | 2016-07-01 | 2018-01-04 | 王胜广 | Coated fluoropolymer particle, and polymer blend and polymer composition containing same |
| CN107586389A (en) * | 2016-07-07 | 2018-01-16 | 中国石油天然气股份有限公司 | Preparation method of fluorine-containing rheological agent |
| CN106947113B (en) * | 2017-04-28 | 2019-05-07 | 山东理工大学 | Fluoropolymer additive and preparation method thereof |
| CN107345098A (en) * | 2017-08-04 | 2017-11-14 | 安徽博泰氟材料科技有限公司 | A kind of aqueous fluorine-carbon paint prepared using emulsifying agent and preparation method thereof |
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| CN101337996A (en) * | 2007-07-04 | 2009-01-07 | 上海聚恒聚合物科技有限公司 | Fluor-containing polymer processing aid, silanes cross-linked polyethylene composition with the processing aid and use of the processing aid |
| CN101531783A (en) * | 2008-12-23 | 2009-09-16 | 上海高分子功能材料研究所 | Delayed cross-linked type silicane cross-linked polyethylene plastic |
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| CN101337996A (en) * | 2007-07-04 | 2009-01-07 | 上海聚恒聚合物科技有限公司 | Fluor-containing polymer processing aid, silanes cross-linked polyethylene composition with the processing aid and use of the processing aid |
| CN101531783A (en) * | 2008-12-23 | 2009-09-16 | 上海高分子功能材料研究所 | Delayed cross-linked type silicane cross-linked polyethylene plastic |
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