CN102286157A - 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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- CN102286157A CN102286157A CN 201110165285 CN201110165285A CN102286157A CN 102286157 A CN102286157 A CN 102286157A CN 201110165285 CN201110165285 CN 201110165285 CN 201110165285 A CN201110165285 A CN 201110165285A CN 102286157 A CN102286157 A CN 102286157A
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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 relative flow rate of melt 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 more than the critical shear rate to certain value, the melt at mouthful die wall place can stick and slides between swing, formation round-robin melt fracture.
All residual micro-moisture in organosilane crosslinked polyethylene and the catalyst masterbatch, also can introduce moisture in the two mixing and the extrusion in addition, make organosilane cross-linked poly-ethylene cable material store and extrusion process in generation hydrolysis-condensation reaction and produce precrosslink easily.The precrosslink reaction makes the molecule quantitative change of organosilane crosslinked polyethylene big, 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,, improve the processing characteristics of organosilane crosslinked polyethylene, prevent mass defect that causes owing to precrosslink and the electric breakdown phenomena that may in cable application, cause to suppress the precrosslink reaction in the organosilane crosslinked polyethylene.
Summary of the invention
The purpose of this invention is to provide a kind of multi-functional fluoropolymer additive.This processing aid is used for silane cross-linked polyolefin to be extruded and adds 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 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 portion is the micropartical of 0.2～1 μ m, described core is made of fluorocarbon polymer, and described shell portion is made of silicone resin, and the weight ratio of described core and shell portion 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 or the multiple monomeric multipolymer of unsaturated fluorochemical monomer.Fluorochemical monomer comprises Fluorine containing olefine homopolymer or multipolymers such as a chlorotrifluoroethylene, vinylidene, R 1216, tetrafluoroethylene, fluoroalkyl ethene, fluoroalkyl fluorovinyl ether, for example 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 fluorocarbon polymer particulate median size 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 softish 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 is meant and contains 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.Add the core emulsion solution then while stirring, the condensation that is hydrolyzed kept the hydrolyzed state stirring reaction 1-10 hour, preferred 2-5 hour, reaction was carried out fully.Add the toluene extraction at last, 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, obtain the final polymer processing aid less than 1%.
Separate out and the polymeric process in order effectively to control, guarantee the stable and size distribution of precipitation particles, the pH value of conditioned reaction liquid adds low quantity of surfactant in advance, and adds the part separant after adding core polymer emulsion and shell portion monomer mixture solution.The pH value of conditioned reaction liquid is 1-7, and preferred 2-6 can control and separate out and the polymeric process.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 the stable and size distribution of precipitation particles, polyoxyethylenated alcohol, fatty alcohol-polyoxyethylene ether, oxyethane propane multipolymer or contain negatively charged ion and nonionogenic tenside such as fluoroalkyl 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 lime 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 MQ silicone resin preferred L/Q=0.5-1.0 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 portion was generally 20: 80～45: 55, was 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 1-20% master batch reprocessing moulding earlier, form goods such as pipe, conduit, wire coating or film.
Used organosilane crosslinked polyethylene for example comprises the organosilane crosslinked polyethylene that 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 height of extruded product.
Embodiment
By the following examples the present invention is further described, but these embodiment only are illustratives, and can not be used to limit 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
Having thermometer, add 6 gram hexamethyldisiloxane in the 250ml there-necked flask of reflux and whipping appts, 0.3ml concentrated hydrochloric acid, 3ml deionized water and 6ml alcoholic acid mixed solution, start stirring then, in 1 hour, drip the poly-FKM of 50 grams then and concentrate dispersion liquid (FKM emulsion L636,30% solid content is available from Solvay Solexis S.P.A).Splash into the hydrolyzing condensation of ethyl silicate of 15 grams then fast, after the hydrolysis 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 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 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 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 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 5% masterbatch respectively with twin screw extruder (L/D40: 1, φ 20 dual-screw pelletizers, Shanghai Bo Lima mechanical means 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, repeat out to continue next sample again behind the equifinality of sample 0 with the crosslinked material of pure silane then.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 the restraining effect of different processing aids to precrosslink according to the gel content testing method of GBT 18474-2001.
Test materials uses the sample of method for preparing.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 prescription 7-19, stable extrude 10 minutes after, the 5-13 that will fill a prescription takes a sample respectively, measures the gel content of different ingredients after extruding respectively 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 the obvious suppression effect to the precrosslink phenomenon in extruding.
4. test 14-22 measures among the present invention fluoropolymer additive to the influence 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 influence of degree of crosslinking.
Claims (10)
1. fluoropolymer additive, it is to be the micropartical of 0.2～1 μ m by the median size that core and shell portion form, described core is made of fluorocarbon polymer, and the MQ silicone resin is contained in described shell portion, and the weight ratio of described core and shell portion is 20: 80～45: 55.
2. fluoropolymer additive as claimed in claim 1, it 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, the weight-average molecular weight of this fluorocarbon polymer is 100,000-10,000,000.
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, described shell portion is the MQ silicone resin of M/Q=0.5～0.9.
5. as claim 1 or 4 described fluoropolymer additives, it is characterized in that the weight ratio of described core and shell portion is 25: 75～40: 60, it is the aggregate of 1 μ m～5mm that the further aggegation of described micropartical becomes particle diameter.
6. the preparation method of the described fluoropolymer additive of claim 1, it is included in in-situ hydrolysis closure agent and silicate monomer mixture under the existence of fluorocarbon polymer corpuscle emulsion.
7. fluoropolymer additive as claimed in claim 1, 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.
8. 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 1-7.
9. the polyethylene composition of the described crosslinked with silicane of claim 8 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.
10. each described fluoropolymer additive application in the organosilane crosslinked polyethylene extrusion moulding among the claim 1-7.
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| CN106947113A (en) * | 2017-04-28 | 2017-07-14 | 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 |
| 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 | A kind of preparation method of fluoropolymer modifier |
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| CN103849092A (en) * | 2013-07-24 | 2014-06-11 | 广科工业股份有限公司 | Composite material micropowder, method for forming same, ceramic coating, and protective coating |
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| CN107586389A (en) * | 2016-07-07 | 2018-01-16 | 中国石油天然气股份有限公司 | A kind of preparation method of fluoropolymer modifier |
| CN106947113A (en) * | 2017-04-28 | 2017-07-14 | 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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