CN1690094A - Superfine polymer rigid filling and its preparation and use - Google Patents
Superfine polymer rigid filling and its preparation and use Download PDFInfo
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- CN1690094A CN1690094A CN 200410017791 CN200410017791A CN1690094A CN 1690094 A CN1690094 A CN 1690094A CN 200410017791 CN200410017791 CN 200410017791 CN 200410017791 A CN200410017791 A CN 200410017791A CN 1690094 A CN1690094 A CN 1690094A
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- ultra
- fine polymer
- rigid filled
- vinylbenzene
- emulsion
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- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000004743 Polypropylene Substances 0.000 claims abstract description 34
- 229920001155 polypropylene Polymers 0.000 claims abstract description 34
- -1 polypropylene Polymers 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 239000000839 emulsion Substances 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000872 buffer Substances 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 239000004159 Potassium persulphate Substances 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- 235000019394 potassium persulphate Nutrition 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 229920001400 block copolymer Polymers 0.000 claims description 8
- 229940096992 potassium oleate Drugs 0.000 claims description 8
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 235000019800 disodium phosphate Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 238000012856 packing Methods 0.000 abstract 2
- 238000011109 contamination Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 17
- 239000000945 filler Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQPPAFWBWFABJ-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-(2-methylprop-2-enoyloxy)ethyl 2-methylprop-2-enoate Chemical compound C=CC1=CC=CC=C1C=C.CC(=C)C(=O)OCCOC(=O)C(C)=C YLQPPAFWBWFABJ-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- Polymerisation Methods In General (AREA)
Abstract
The invention provides an ultra-fine polymer rigid packing, the method for producing it, and its application in producing polypropylene composite. The benefit effect mainly lies in: such packing is of adjustable grain diameter, fine coarseness, and good rigidness, good dispersity, white product; the produce is of reasonable technique, simple method, low temperature, and slight environmental contamination; can be used for producing polypropylene composite, with good toughening effect, and easy to disperse.
Description
(1) technical field
It is rigid filled and preparation method thereof to the present invention relates to a kind of ultra-fine polymer, and the rigid filled application in the preparation polypropylene composite material of this ultra-fine polymer.
(2) background technology
The more employing of the particle diameter of the latex particle of letex polymerization at present changes the consumption of emulsifying agent and controls, the rigid filled particle synthetic of ultra-fine polymer control condition does not still have detailed research, the amount of initiator, linking agent to the rigid filled particle of ultra-fine polymer form the particle of speed, formation whether sticking and and the rigidity of particle bigger influence is arranged, it influences dispersion and enhancing in polymkeric substance too.Inorganic nano-particle is because agglomeration strength is big, and difficult hot melt in the short period of time is disperseed in processing preferably, and its application is restricted.
Inorganic, organic nanocomposite can improve the dispersiveness of nanoparticle in polymkeric substance largely, and the normal method that adopts has: inorganic nano-particle is coated with the machine thing; Embed organism between the lamella inorganic nano material, most representative is that Japan is at the 1987 PA6/ clay nano mixtures that make.Utilize the rigid filled particle surface tension force of ultra-fine polymer little, good with polypropylene compatible, with it strengthen, tenacity-increased profax, can easily not reunite just like inorganic nano-filler, difficult dispersive shortcoming, its surface is easily modified, the preparation method is simple, cost is more cheap than most of inorganic nano-fillers, easily promotes in actual applications.
(3) summary of the invention
The present invention is that a kind of technology is reasonable, method is simple in order to provide, and makes adjustable rigid filled particle of ultra-fine polymer of granularity and preparation method thereof, and the application of the rigid filled particle of described ultra-fine polymer in the preparation polypropylene composite material.
For reaching the goal of the invention the technical solution adopted in the present invention be:
A kind of ultra-fine polymer is rigid filled, and the rigid filled quality of described ultra-fine polymer is composed as follows:
Vinylbenzene 20～50%, linking agent 1～5%, water 45～76%, buffer reagent 0.2～1.0%, initiator 0.05～2.0%, emulsifying agent 0.5～3%.
Described linking agent is one of following or its mixture:
1. divinylbenzene, 2. Ethylene glycol dimethacrylate (EGDM), 3. dicyclopentadiene, 4. triallyl isocyanurate (TAIC).
Described buffer reagent is one of following:
1. sodium bicarbonate, 2. SODIUM PHOSPHATE, MONOBASIC, 3. trisodium phosphate.
Described initiator is one of following:
1. Potassium Persulphate, 2. Sodium Persulfate, 3. ammonium persulphate, 4. hydrogen peroxide.
Described emulsifying agent is one of following or its mixture:
1. potassium oleate, 2. sodium oleate, 3. sodium lauryl sulphate, 4. Sodium dodecylbenzene sulfonate, 5. OP-10.
Described method is carried out as follows:
Vinylbenzene, emulsifying agent, linking agent, buffer reagent, the water of recipe quantity are added pre-emulsification in the reactor, part pre-emulsion is stayed 1/4～1/2 the initiator that adds recipe quantity in the reactor and is warming up to 60～80 ℃, drips remaining pre-emulsion then, and evenly adds the aqueous solution of residue initiator, dropwise back insulation 0.5～2 hour, be warming up to 80～95 ℃, constant temperature is 1～2 hour again, cooling, breakdown of emulsion, washing is filtered, and it is rigid filled that vacuum-drying gets ultra-fine polymer.
The rigid filled quality of described ultra-fine polymer is composed as follows:
Vinylbenzene 40%, potassium oleate 2%, divinylbenzene 2.4%, sodium hydrogen phosphate 0.5%, distilled water 54.7%, Potassium Persulphate 0.4%; Described method is carried out as follows: vinylbenzene, potassium oleate, divinylbenzene, sodium hydrogen phosphate, distilled water are added pre-emulsification in the reactor, part pre-emulsion is stayed 1/4～1/2 the Potassium Persulphate that adds recipe quantity in the reactor and is warming up to 70 ℃, drip remaining pre-emulsion then, and the aqueous solution of evenly adding residue Potassium Persulphate, dropwise back insulation 0.5～2 hour, be warming up to 85 ℃, constant temperature is 1～2 hour again, cooling, breakdown of emulsion, washing is filtered, and it is rigid filled that vacuum-drying gets ultra-fine polymer.
Described ultra-fine polymer is rigid filled to can be used to prepare polypropylene composite material: with mass content be that 1～10% ultra-fine polymer is rigid filled, 76～96% polypropylene, 1～15% compatilizer disperse, mix, extrude through 180～200 ℃ of melting heats, makes polypropylene composite material.Described compatilizer is one of following or its mixture:
1. vinylbenzene, butadiene block copolymer (SBS), 2. vinylbenzene, butadiene random copolymer elastomerics (BS), 3. polypropylene grafted vinylbenzene (PP-g-St).
Beneficial effect of the present invention is mainly reflected in: the rigid filled particle diameter of (1) gained ultra-fine polymer is adjustable, fine size, rigidity big, good dispersity, product look white; (2) preparation industry rationally, method is simple, temperature of reaction is low, environmental pollution is little; (3) be applied to the preparation toughening effect of polypropylene composite material good, make it easier dispersion.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment:
Embodiment 1～4: the preparation that ultra-fine polymer is rigid filled
Respectively with 500g, 400g, 300g, 200g vinylbenzene, 18g emulsifying agent potassium oleate, 20g linking agent Ethylene glycol dimethacrylate, 5g buffer reagent NaHCO
3, 453g, 553g, 653g, 753g distilled water water adds pre-emulsification in the reactor, part pre-emulsion is stayed the interior 1g of adding of reactor Potassium Persulphate initiator and is warming up to 70 ℃, drip the remaining pre-emulsion and the aqueous solution that contains 3g Potassium Persulphate initiator then, dropwise back insulation 1 hour, be warming up to 85 ℃, constant temperature is 1 hour again, cooling, and it is as follows to measure the size of particles result:
| Embodiment | ????1 | ????2 | ????3 | ????4 |
| Concentration of styrene, wt% | ????50 | ????40 | ????30 | ????20 |
| Size distribution/um D50/% D90/% S.S.A/ (m 2/c.c) | ????0.80～1.23 ????0.84 ????0.99 ????5.90 | ????0.75～0.90 ????0.77 ????0.84 ????7.06 | ????0.60～0.94 ????0.65 ????0.73 ????9.79 | ????0.46～0.55 ????0.47 ????0.51 ????12.81 |
Embodiment 5～9: the preparation that ultra-fine polymer is rigid filled
Respectively with 300g vinylbenzene, 20g different sorts emulsifying agent, 15g linking agent Ethylene glycol dimethacrylate, 5g buffer reagent NaH
2PO
4, 656g water adds pre-emulsification in the reactor, part pre-emulsion is stayed the interior 1g of adding of reactor ammonium persulfate initiator and is warming up to 80 ℃, drip the remaining pre-emulsion and the aqueous solution that contains the 3g ammonium persulfate initiator then, dropwise back insulation 0.5 hour, be warming up to 85 ℃, constant temperature is 1 hour again, cooling, and it is as follows to measure the size of particles result:
| Embodiment | ????5 | ????6 | ????7 | ????8 | ????9 |
| OP-10: Sodium dodecylbenzene sulfonate: sodium lauryl sulphate | ????4∶1∶1 | ????3∶2∶1 | ????3∶1∶2 | ????2∶2∶2 | ????1∶2∶3 |
| Size distribution/um D50/% D90/% S.S.A/ (m 2/c.c) | ????0.60～0.83 ????0.74 ????0.99 ????8.90 | ????0.45～0.75 ????0.57 ????0.70 ????10.6 | ????0.37～0.63 ????0.45 ????0.61 ????13.9 | ????0.87～1.01 ????0.97 ????1.05 ????6.81 | ????0.92～1.35 ????1.05 ????1.24 ????5.94 |
Embodiment 10～14: the preparation that ultra-fine polymer is rigid filled
Respectively with 250g vinylbenzene, and the compound emulsifying agent of 10g, 15g, 20g, 25g, 30g (OP-10: Sodium dodecylbenzene sulfonate: sodium laurylsulfonate=4: 1: 1), 25g linking agent divinylbenzene, 10g buffer reagent NaH
2PO
4701g, 696g, 691g, 686g, 681g distilled water add pre-emulsification in the reactor, part pre-emulsion is stayed the interior 1g of adding of reactor ammonium persulfate initiator and is warming up to 80 ℃, drip the remaining monomer pre-emulsion and the 3g ammonium persulfate initiator aqueous solution then, dropwise back insulation 0.5 hour, be warming up to 85 ℃, constant temperature is 1 hour again, cooling, and it is as follows to measure the size of particles result:
| The composite emulsifying agent concentration, wt% | ????1 | ????1.5 | ????2.0 | ????2.5 | ????3.0 |
| Size distribution/um D50/% D90/% S.S.A/ (m 2/c.c) | ????0.90～1.15 ????1.00 ????1.10 ????6.94 | ????0.75～0.97 ????0.67 ????0.82 ????7.90 | ????0.49～0.72 ????0.57 ????0.70 ????12.6 | ????0.39.～0.53 ????0.45 ????0.51 ????14.5 | ????0.60～0.83 ????0.74 ????0.99 ????10.6 |
Embodiment 15～18: the preparation that ultra-fine polymer is rigid filled
With 400g vinylbenzene, 22g emulsifying agent sodium oleate, 25g linking agent triallyl isocyanurate, 5g buffer reagent NaH
2PO
4, 542g distilled water adds pre-emulsification in the reactor, part pre-emulsion is stayed the various initiators of the interior 1g of adding of reactor and is warming up to 70 ℃, drip the remaining pre-emulsion and the aqueous solution that contains the various initiators of 5g then, dropwise back insulation 0.5 hour, be warming up to 90 ℃, constant temperature is 1 hour again, cooling, and it is as follows to measure the size of particles result:
| Embodiment | ????15 | ????16 | ????17 | ????18 |
| Initiator | Potassium Persulphate | Sodium Persulfate | Ammonium persulphate | Hydrogen peroxide |
| Size distribution/um D50/% D90/% S.S.A/ (m 2/c.c) | ????0.50～0.67 ????0.57 ????0.64 ????9.94 | ????0.55?～0.77 ????0.67 ????0.71 ????9.90 | ????0.59～0.72 ????0.67 ????0.70 ????8.69 | ????0.69.～0.83 ????0.75 ????0.79 ????8.11 |
Embodiment 19～22: the preparation that ultra-fine polymer is rigid filled
Sodium laurylsulfonate=3: 2: 1), 25g linking agent dicyclopentadiene, 3g buffer reagent NaH with 300g vinylbenzene, 22g compound emulsifying agent (OP-10: Sodium dodecylbenzene sulfonate:
2PO
4, the 640g deionized water adds pre-emulsification in the reactor, part pre-emulsion is stayed the interior difference amount initiator hydrogen peroxide that add of reactor and is warming up to 60 ℃, drip remaining pre-emulsion and different amount initiator hydrogen peroxide then, dropwise back insulation 0.5 hour, be warming up to 80 ℃, constant temperature is 1 hour again, cooling, and it is as follows to measure the size of particles result:
| Embodiment | ????19 | ????20 | ????21 | ????22 |
| Initiator wt% | ????0.1 ????0.5 | ????0.1 ????0.7 | ????0.1 ????0.9 | ????0.1 ????1.1 |
| Size distribution/um D50/% D90/% S.S.A/ (m 2/c.c) | ????0.50～0.67 ????0.57 ????0.64 ????12.94 | ????0.51～0.71 ????0.67 ????0.70 ????12.30 | ????0.39～0.52 ????0.41 ????0.49 ????14.8 | ????0.55～0.77 ????0.75 ????0.76 ????11.11 |
Embodiment 23～26: the preparation that ultra-fine polymer is rigid filled
With 400g vinylbenzene, 20g emulsifying agent sodium oleate, the different linking agents of 14g, 5g buffer reagent NaH
2PO
4, 560g distilled water adds pre-emulsification in the reactor, part pre-emulsion is stayed the interior 0.5g of adding of reactor initiator potassium persulfate and is warming up to 70 ℃, drip the remaining pre-emulsion and the aqueous solution that contains the 1g initiator potassium persulfate then, dropwise back insulation 0.5 hour, be warming up to 90 ℃, constant temperature is 1 hour again, cooling, and it is as follows to measure the size of particles result:
| Embodiment | ????23 | ????24 | ????25 | ????26 |
| Linking agent | Ethylene glycol dimethacrylate | Divinylbenzene | Triallyl isocyanurate | Dicyclopentadiene |
| Size distribution/um D50/% D90/% S.S.A/ (m 2/c.c) | ????0.40～0.57 ????0.47 ????0.54 ????13.94 | ????0.45～0.64 ????0.54 ????0.62 ????12.90 | ????0.49～0.62 ????0.53 ????0.60 ????11.69 | ????0.69～0.80 ????0.72 ????0.78 ????8.11 |
Embodiment 27～30: the preparation that ultra-fine polymer is rigid filled
With 400g vinylbenzene, 20g emulsifying agent potassium oleate, the linking agent divinylbenzene 16g of different amounts, 24g, 32g, 40g, 5g buffer reagent NaH
2PO
4555g, 547g, 539g, 531g distilled water add pre-emulsification in the reactor, part pre-emulsion is stayed the interior 1.0g of adding of reactor initiator potassium persulfate and is warming up to 70 ℃, drip the remaining pre-emulsion and the aqueous solution that contains the 3g initiator potassium persulfate then, dropwise back insulation 0.5 hour, be warming up to 90 ℃, constant temperature is 1 hour again, cooling, it is as follows to measure the size of particles result:
| Embodiment | ????27 | ????28 | ????29 | ????30 |
| The divinylbenzene amount, g | ????16 | ????24 | ????32 | ????40 |
| Size distribution/um D50/% D90/% S.S.A/ (m 2/c.c) | ????0.42～0.56 ????0.49 ????0.53 ????12.90 | ????0.41～0.54 ????0.47 ????0.50 ????14.70 | ????0.49～0.62 ????0.53 ????0.60 ????11.69 | ????0.59～0.81 ????0.67 ????0.74 ????8.23 |
Embodiment 31～35: the preparation of polypropylene composite material
Rigid filled with 10g embodiment 28 gained ultra-fine polymers is that filler is respectively at mixing with the polypropylene grafted vinylbenzene of compatilizer of 950g, 930g, 910g, 890g, 870g polypropylene and 20g, the butadiene block copolymer that adds 20g, 40g, 60g, 80g, 100g respectively, disperse, mix, extrude through 180～200 ℃ of melting heats, make a kind of new polypropylene composite material, measure its mechanical property, the result is as follows:
| Embodiment | ??31 | ??32 | ??33 | ??34 | ??35 |
| Butadiene block copolymer, wt% | ??2 | ??4 | ??6 | ??8 | ??10 |
| Tensile strength/Mpa tensile modulus/Mpa elongation at break/% | ??31.4 ??854 ??618 | ??26.3 ??810 ??890 | ??25.5 ??842 ??855 | ??25.2 ??816 ??940 | ??26.1 ??723 ??896 |
| Simple beam impact strength/Mpa | ??24 | ??39 | ??45 | ??52 | ??48 |
Embodiment 36～40: the preparation of polypropylene composite material
Respectively with 10g, 30g, 50g, 70g, 90g embodiment 28 gained ultra-fine polymers are rigid filled mixes with polypropylene grafted vinylbenzene of compatilizer and the 50g butadiene block copolymer of 890g, 870g, 850g, 830g, 810g polypropylene and 50g, disperse, mix, extrude through 180-200 ℃ of melting heat, make a kind of new polypropylene composite material, measure its mechanical property, the result is as follows:
| Embodiment | ????36 | ????37 | ????38 | ????39 | ????40 |
| Crosslinked polystyrene, wt% | ????1 | ????3 | ????5 | ????7 | ????9 |
| Tensile strength/Mpa tensile modulus/Mpa elongation at break/% | ????30.4 ????894 ????618 | ????30.3 ????890 ????590 | ????28.5 ????942 ????555 | ????25.2 ????816 ????540 | ????26.1 ????723 ????896 |
| Simple beam impact strength/Mpa | ????35 | ????41 | ????51 | ????45 | ????48 |
Embodiment 41～44: the preparation of polypropylene composite material
Rigid filled with 100g embodiment 28 gained ultra-fine polymers as the different compatilizers of filler with 780g polypropylene and 120g, through 180-200 ℃ of fusion, dissipation of heat, mix, extrude, make a kind of new polypropylene composite material, measure its mechanical property, the result is as follows:
| Embodiment | ?41 | ?42 | ?43 | ????44 |
| Compatilizer | Polypropylene grafted vinylbenzene | The butadiene random copolymer elastomerics | Butadiene block copolymer | The polypropylene grafted vinylbenzene of 6wt% butadiene block copolymer+6wt% |
| Tensile strength/Mpa tensile modulus/Mpa elongation at break/% | ?30.4 ?894 ?618 | ?28.3 ?790 ?590 | ?28.5 ?812 ?555 | ????29.1 ????823 ????896 |
| Simple beam impact strength/Mpa | ?35 | ?32 | ?41 | ????48 |
Embodiment 45,46: the preparation of polypropylene composite material
Mix with the polypropylene grafted vinylbenzene of the compatilizer of 900g different sorts polypropylene and 20g as filler with 60g embodiment 28 gained ultra-fine polymers are rigid filled, the butadiene block copolymer that adds 20g, disperse, mix, extrude through 180-200 ℃ of melting heat, make a kind of new polypropylene composite material, measure its mechanical property, the result is as follows:
| Embodiment | ????45 | ????46 |
| Polyacrylic model | Homo-polypropylene F401 | Co-polypropylene T30S |
| Tensile strength/Mpa tensile modulus/Mpa elongation at break/% | ????34.4 ????1332 ????518 | ????32.3 ????1123 ????890 |
| Simple beam impact strength/Mpa | ????25 | ????54 |
Claims (10)
1. a ultra-fine polymer is rigid filled, it is characterized in that described ultra-fine polymer is rigid filled
Quality is composed as follows:
Vinylbenzene 20～50%
Linking agent 1～5%
Water 45～76%
Buffer reagent 0.2～1.0%
Initiator 0.05～2.0%
Emulsifying agent 0.5～3%.
2. ultra-fine polymer as claimed in claim 1 is rigid filled, it is characterized in that described linking agent is one of following or its mixture:
1. divinylbenzene, 2. Ethylene glycol dimethacrylate, 3. dicyclopentadiene, 4. triallyl isocyanurate.
3. ultra-fine polymer as claimed in claim 1 is rigid filled, it is characterized in that described buffer reagent is one of following:
1. sodium bicarbonate, 2. SODIUM PHOSPHATE, MONOBASIC, 3. trisodium phosphate.
4. ultra-fine polymer as claimed in claim 1 is rigid filled, it is characterized in that described initiator is one of following:
1. Potassium Persulphate, 2. Sodium Persulfate, 3. ammonium persulphate, 4. hydrogen peroxide.
5. ultra-fine polymer as claimed in claim 1 is rigid filled, it is characterized in that described emulsifying agent is one of following or its mixture:
1. potassium oleate, 2. sodium oleate, 3. sodium lauryl sulphate, 4. Sodium dodecylbenzene sulfonate, 5. OP-10.
6. prepare the rigid filled method of ultra-fine polymer as claimed in claim 1, it is characterized in that described method carries out as follows:
Vinylbenzene, emulsifying agent, linking agent, buffer reagent, the water of recipe quantity are added pre-emulsification in the reactor, part pre-emulsion is stayed 1/4～1/2 the initiator that adds recipe quantity in the reactor and is warming up to 60～80 ℃, drips remaining pre-emulsion then, and evenly adds the aqueous solution of residue initiator, dropwise back insulation 0.5～2 hour, be warming up to 80～95 ℃, constant temperature is 1～2 hour again, cooling, breakdown of emulsion, washing is filtered, and it is rigid filled that vacuum-drying gets ultra-fine polymer.
7. the rigid filled preparation method of ultra-fine polymer as claimed in claim 6 is characterized in that the rigid filled quality of described ultra-fine polymer is composed as follows:
Vinylbenzene 40%
Potassium oleate 2%
Divinylbenzene 2.4%
Sodium hydrogen phosphate 0.5%
Distilled water 54.7%
Potassium Persulphate 0.4%
Described method is carried out as follows:
Vinylbenzene, potassium oleate, divinylbenzene, sodium hydrogen phosphate, distilled water are added pre-emulsification in the reactor, part pre-emulsion is stayed 1/4～1/2 the Potassium Persulphate that adds recipe quantity in the reactor and is warming up to 70 ℃, drips remaining pre-emulsion then, and evenly adds the aqueous solution of residue Potassium Persulphate, dropwise back insulation 0.5～2 hour, be warming up to 85 ℃, constant temperature is 1～2 hour again, cooling, breakdown of emulsion, washing is filtered, and it is rigid filled that vacuum-drying gets ultra-fine polymer.
8. the application in the preparation polypropylene composite material that ultra-fine polymer as claimed in claim 1 is rigid filled.
9. the application in the preparation polypropylene composite material that ultra-fine polymer as claimed in claim 8 is rigid filled, it is characterized in that described application be with mass content be that 1～10% ultra-fine polymer is rigid filled, 76～96% polypropylene, 1～15% compatilizer disperse, mix, extrude through 180～200 ℃ of melting heats, makes polypropylene composite material.
10. ultra-fine polymer as claimed in claim 8 is rigid filled in the application of preparation in the polypropylene composite material, it is characterized in that described compatilizer is one of following or its mixture:
1. vinylbenzene, butadiene block copolymer
2. vinylbenzene, butadiene random copolymer elastomerics
3. polypropylene grafted vinylbenzene.
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| CN 200410017791 CN1690094A (en) | 2004-04-21 | 2004-04-21 | Superfine polymer rigid filling and its preparation and use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358197A (en) * | 2019-08-07 | 2019-10-22 | 联塑科技发展(武汉)有限公司 | A kind of random copolymerization polypropylene pipe and preparation method thereof of novel enhanced toughening |
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2004
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358197A (en) * | 2019-08-07 | 2019-10-22 | 联塑科技发展(武汉)有限公司 | A kind of random copolymerization polypropylene pipe and preparation method thereof of novel enhanced toughening |
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