CN100448926C - Polyolefine toughening modifier and its production - Google Patents
Polyolefine toughening modifier and its production Download PDFInfo
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Abstract
A polyolefin toughening modifier and its production are disclosed. It consists of vinyl-vinyl acetate copolymer 60-80wt% and low-density polyethylene 20-40wt%, the alcoholysis degree is 80-90wt%. It has better toughness and rigidity and can be used for inorganic filler.
Description
Technical field
The present invention is used for polyolefin modified properties-correcting agent and preparation method thereof, specifically, is a kind of increase polyolefine toughness and inflexible properties-correcting agent and preparation method thereof.
Background technology
Polypropylene is a kind of good comprehensive properties thermoplastic resin, except that having favorable mechanical performance, processing characteristics and optical property, also has cheap advantage, is one of material with fastest developing speed in recent years.People have carried out number of research projects at the polyacrylic shock strength of raising, rigidity, heat-drawn wire and other various aspect of performances.Particularly aspect the polyacrylic shock resistance of raising, developed such as elastic body toughening systems such as EPDM/PP, SBS/PP and POE/PP.Aspect raising polypropylene articles rigidity, successively in the PP matrix material, add mineral fillers such as lime carbonate, talcum powder, mica powder, wollastonite.For increasing substantially the rigidity of material, even adopt the big fillers of length-to-diameter ratio such as glass fibre, potassium titanate crystal whisker to strengthen its rigidity.Above-mentioned these modified methods only can significantly improve polyacrylic performance from a certain or several aspects, the difficult performance that comprehensively improves material on the whole.
CN01133694C discloses a kind of novel thermoplastic elastomer and preparation method.This elastomerics cross-linked composite that to be ethylene-octene copolymer form with high density polyethylene(HDPE) and inorganic nano material, can be when significantly improving the shock resistance of homo-polypropylene, keep its tensile strength and rigidity to greatest extent, add mineral filler in this system further to significantly improve the rigidity of material but be difficult in.
Ethylene-vinyl acetate copolymer (EVA) is a kind of low-pole polymkeric substance, has toughness preferably.USP5 has adopted 65～75% EVA and mineral filler, whipping agent, linking agent blend granulation among 560, the 877 disclosed EVA sole preparation technologies, the sheet material that makes is through the hot-pressing and foaming moulding, and re-shearing becomes sole.USP5,747,559 and USP6,197,848 have all introduced the crosslinked polymer thing that contains 16～55%EVA and ethylene-propylene rubber(EPR) (EPR), terpolymer EP rubber (EPDM), contain 24～74% the treated weighting material that is selected from carbon black, graphite or metal oxide in this cross-linking agent, be used to prepare electric wire.
US6,258,862B1 discloses the composition of a kind of polyolefine and EVA, all contains a certain amount of EVA and propene polymer in its uncrosslinked component and the linked, and linking agent adopts organo-peroxide.Said composition is mainly used in preparation automobile foam sheet, helps foaming.
Summary of the invention
The purpose of this invention is to provide a kind of polyolefine toughening modifier, this properties-correcting agent can make effective filling inorganics in the polyolefin products, increases the toughness of polyolefin products.
Polyolefine toughening modifier provided by the invention comprises the cross-linking agent that contains following component of partial alcoholysis:
Ethylene-vinyl acetate copolymer 60～80 quality %
New LDPE (film grade) 20～40 quality %
The alcoholysis degree of described cross-linking agent is 80～90%.
Polyolefine toughening modifier provided by the invention carries out partial alcoholysis with the cross-linking agent of ethylene-vinyl acetate copolymer and new LDPE (film grade) and makes.This properties-correcting agent is used for the toughening modifying of homo-polypropylene, allows to add a certain amount of mineral filler in modified system, significantly improves the rigidity and the toughness of material, reduces cost, and can keep tensile strength preferably.Compare with general rubber-like plasticized modifier EPDM, EPR, POE, SBS, SEBS etc., toughening effect is more remarkable, and is stronger with the consistency of mineral filler.
Embodiment
The present invention forms cross-linking agent with ethylene-vinyl acetate copolymer and new LDPE (film grade) blend, and also can further contain the inorganics of certain particle size in the described cross-linking agent.Described multipolymer is carried out partial alcoholysis, increase oh group wherein, can significantly improve the affinity of itself and polar material.With this properties-correcting agent to polyolefine carry out that modification obtains material modified, can effectively absorb and put on material modified impact energy, obtain significant toughening effect with less consumption.In addition, because the affinity of this properties-correcting agent and mineral filler significantly strengthens, a large amount of mineral fillers is filled in permission in modified system, so also can make the material after the modification have higher rigidity, can not add the problem of mineral filler when having solved ethylene-octene copolymer (POE) toughened master batch modification homo-polypropylene to a certain extent simultaneously.
The inorganics that also contains 1～15 quality % in the cross-linking agent of ethylene-vinyl acetate copolymer of the present invention and new LDPE (film grade), add behind the inorganics that the content of ethylene-vinyl acetate copolymer is 60～80 quality % in the described cross-linking agent, the content of new LDPE (film grade) is 18～35 quality %.
Degree of crosslinking before the cross-linking agent alcoholysis of the present invention is 30～50%.
The melting index of described ethylene-vinyl acetate copolymer is 2～60 grams/10 minutes, preferred 5～10 grams/10 minutes, and wherein the content of vinyl acetate is 10～50 quality %, preferred 20～30 quality %.
The density of described new LDPE (film grade) is 0.91～0.93 gram per centimeter
3, melting index is 1～5 gram/10 minutes.
Described inorganics granularity is 0.01～5.0 micron, preferred 0.1～1.0 micron.Inorganics preferably talc powder, barium sulfate, titanium dioxide, lime carbonate or white carbon black.
Described polyolefine optimization polypropylene.
The preparation method of properties-correcting agent provided by the invention comprises the steps:
(1) premix: it is 50～100 rev/mins low speed mixer that ethylene-vinyl acetate copolymer, new LDPE (film grade) are added rotating speed successively, and 20～40 ℃ of pre-mixings slowly add linking agent again and mix preferred 5～8 minutes of mixing time;
(2) crosslinked: mixed material of (1) step is added the homodromy parallel twin screw extruder, and controlling each section extrusion temperature is 150～250 ℃, and screw speed is 150～250 rev/mins, and the feeding machine rotating speed is 20～50 rev/mins, obtains the cross-linking agent particle;
(3) partial alcoholysis: the cross-linking agent particle is added in the aqueous solution of the potassium hydroxide that contains 1.0～3.0 quality %, partial alcoholysis is carried out in 50～70 ℃ of reactions, and the control alcoholysis degree is 80～90%.
Also can further contain organic/inorganic substance during described (1) step premix is reinforced, when reinforced, it is 50～100 rev/mins low speed mixer that ethylene-vinyl acetate copolymer, new LDPE (film grade) and inorganics are added rotating speed successively.
Described inorganics preferably talc powder, barium sulfate, titanium dioxide, lime carbonate or white carbon black.
The preferred ditertiary butyl peroxide of described linking agent or 2, the 5-2.The dosage of linking agent is 0.1～1.0 quality % of blend material total amount.
Described (3) step carries out the aqueous solution of the potassium hydroxide that the cross-linking agent partial alcoholysis uses and the mass ratio of cross-linking agent is 2.1～14.0: 1, preferred 3～6 hours of alcoholysis time.
The degree of crosslinking of above-mentioned copolymerization represents with gel content, and promptly gel content accounts for the per-cent of raw material ethylene-vinyl acetate copolymer and new LDPE (film grade) total amount in the multipolymer.
The alcoholysis degree of described ethylene-vinyl acetate copolymer/polyethylene crosslinking substance in low density represents that with alcoholysis degree i.e. alcoholysis depickling amount accounts for the molar percentage of vinyl acetate in the ethylene-vinyl acetate copolymer.Alcoholysis degree adopts that hydrolyzable moiety is not with KOH solution complete hydrolysis to described multipolymer, and excessive KOH calculates the amount of the whole hydrolysis of multipolymer with certain density hydrochloric acid back titration, calculates alcoholysis degree more thus.
Properties-correcting agent provided by the invention is applicable to polyolefine, especially polyacrylic toughening modifying, properties-correcting agent that adds during modification and polyolefinic mass ratio are 0.06～0.2: 1, also can add inorganic filler during modification, and inorganic filler and polyolefinic mass ratio are 0.2～0.5: 1.
The method for preparing modified polyolefin adopts conventional method preparation: earlier properties-correcting agent and polyolefine are mixed in proportion, preferably add inorganic filler therein, and then adding oxidation inhibitor stirs.It is 500～800 rev/mins high-speed mixer that mixture is added rotating speed, and 20～40 ℃ were mixed 5～8 minutes, and added granulation in the homodromy parallel twin screw extruder again.The granulation process condition is: 195～235 ℃ of each section of control forcing machine temperature, 150～250 rev/mins of screw speeds, 20～50 rev/mins of feeding machine rotating speeds.
Further specify the present invention below by example, but the present invention is not limited to this.
The degree of crosslinking of ethylene-vinyl acetate copolymer/polyethylene crosslinking substance in low density and alcoholysis degree adopt following method to measure in the example:
1, degree of crosslinking: in Soxhlet extractor, add ethylene-vinyl acetate copolymer/polyethylene crosslinking substance in low density and xylene solvent, azeotropic extracting 6 hours, dry insolubles under 80 ℃, 0.09MPa condition is calculated as follows degree of crosslinking.
Degree of crosslinking=(insolubles net weight/sample gross weight) * 100%
2, alcoholysis degree: taking by weighing a certain amount of ethylene-vinyl acetate copolymer/polyethylene crosslinking substance in low density, is N with concentration
1(mol/L), volume be V (L) potassium hydroxide solution 50～70 ℃ of alcoholysis 5 hours, the volume ratio of used potassium hydroxide solution and cross-linking agent is 5: 1, replenishes the KOH solution V of same concentration then
1(L), guaranteeing that KOH is excessive, continue reaction 3 hours in above-mentioned alcoholysis conditions, make ethylene-vinyl acetate copolymer component complete alcoholysis, is N with concentration then
2(mol/L) hydrochloric acid back titration is an indicator with the phenolphthalein solution, and the hydrochloric acid volume of consumption is V
2(L).
Example 1
The cross-linking agent of preparation partial alcoholysis of the present invention.
(1) premix: getting 2100 gram vinyl acetate (VA) content is 28.0%, and melting index is/10 minutes ethylene-vinyl acetate (EVA) multipolymer of 6.2 grams (Beijing Organic Chemical Plant produces, trade mark EVA28-6), and 900 gram density are 0.923 gram per centimeter
3, melting index is/10 minutes a new LDPE (film grade) of 3.1 grams (plastic molding and processing plant of Qilu Petrochemical company produces, trade mark TN26), 9 gram linking agent DTBP (ditertiary butyl peroxide).Earlier with EVA28-6 and TN26 in rotating speed is 60 rev/mins low speed mixer, mixed 3 minutes in 25 ℃, add DTBP again and mixed 8 minutes, form mixture.
(2) crosslinked: that (1) step mixture is added granulation in the cocurrent and parallel twin screw extruder.Extruder temperature is distributed as, 160 ℃ in a district, 180 ℃ in two districts, 190 ℃ in three districts, 190 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 190 ℃ in seven districts, 185 ℃ in eight districts.200 rev/mins of screw speeds, 30 rev/mins of feeding machine rotating speeds.Cold drawn pelletizing, ethylene-vinyl acetate copolymer/polyethylene crosslinking substance in low density, recording degree of crosslinking is 28.0%.
(3) partial alcoholysis: adding 5620 gram KOH content in reactor is the hot water of 2.0 quality %, add the cross-linking agent that 1000 gram (2) steps made again, partial alcoholysis was carried out in reaction in 3.5 hours under 65 ℃, 70 rev/mins stirring velocity, 105 ℃ of dry modifier As that get, it is formed and alcoholysis degree sees Table 1.
Example 2
Method by example 1 prepares properties-correcting agent B, and different is that the linking agent that adds in (1) step is two " 2, the 5 " vulcanizing agents ((2, the 5-2) of 9 grams.Composition and the alcoholysis degree of properties-correcting agent B see Table 1.
Example 3
Method by example 1 prepares properties-correcting agent C, and different is to add two " 2, the 5 " vulcanizing agents of 15 grams in (1) step.Composition and the alcoholysis degree of properties-correcting agent C see Table 1.
Example 4
Method by example 1 prepares properties-correcting agent D, and different is in (1), adds earlier 1890 gram EVA and 960 gram low density PEs, adds 150 gram particle degree again and be 3～5 microns barium sulfate, and two " 2, the 5 " vulcanizing agents of 15 grams carry out premix.Composition and the alcoholysis degree of the properties-correcting agent D that obtains see Table 1.
Example 5
Method by example 1 prepares properties-correcting agent E, in different is (1) step, adds 1890 gram EVA and 960 gram low density PEs earlier, adds 150 gram particle degree again and be 3～5 microns talcum powder, and two " 2, the 5 " vulcanizing agents of 15 grams carry out premix.Composition and the alcoholysis degree of the properties-correcting agent E that obtains see Table 1.
Example 6
Method by example 1 prepares properties-correcting agent F, in different is (1) step, adds 1800 gram EVA and 900 gram low density PEs earlier, adds 300 gram particle degree again and be 3～5 microns talcum powder, and two " 2, the 5 " vulcanizing agents of 15 grams carry out premix.Composition and the alcoholysis degree of the properties-correcting agent F that obtains see Table 1.
Example 7
Method by example 1 prepares properties-correcting agent G, in different is (1) step, adds 1890 gram EVA and 960 gram low density PEs earlier, adds 150 gram particle degree again and be 1～3 micron titanium dioxide, and two " 2, the 5 " vulcanizing agents of 15 grams carry out premix.Composition and the alcoholysis degree of the properties-correcting agent G that obtains see Table 1.
Example 8
Method by example 1 prepares properties-correcting agent H, in different is (1) step, adds 1890 gram EVA and 960 gram low density PEs earlier, adds 150 gram particle degree again and be 3～5 microns lime carbonate, and two " 2, the 5 " vulcanizing agents of 15 grams carry out premix.Composition and the alcoholysis degree of the properties-correcting agent H that obtains see Table 1.
Example 9
Method by example 1 prepares properties-correcting agent I, in different is (1) step, adds 1890 gram EVA and 960 gram low density PEs earlier, adds 150 gram particle degree again and be 1～3 micron white carbon black, and two " 2, the 5 " vulcanizing agents of 15 grams carry out premix.Composition and the alcoholysis degree of the properties-correcting agent I that obtains see Table 1.
Comparative Examples 1
Method by example 1 prepares properties-correcting agent M, different is (1) step does not add linking agent during premix, material only carries out blend behind the premix in (2) step, and composition and the alcoholysis degree of the blend M of the ethylene-vinyl acetate copolymer/new LDPE (film grade) of the partial alcoholysis that obtains see Table 1.
Example 10～18
Following case expedition properties-correcting agent of the present invention is to polyacrylic toughness reinforcing performance.
Properties-correcting agent, 300 gram talcum powder, 900 gram homo-polypropylene (F401), 100 gram Co-polypropylene (K8303), 2 gram antioxidant 1010s and the 3 gram oxidation inhibitor 168 of getting 100 gram the present invention preparations add rotating speeds be in 500 rev/mins the high-speed mixer 20～40 ℃ be mixed 5 minutes to evenly, add in the homodromy parallel twin screw extruder, extruding pelletization under 200 rev/mins rotating speeds, 195～235 ℃ condition obtains toughness reinforcing rigid polypropylene blend.Used properties-correcting agent numbering of each example and modified polypropene product performance see Table 2.
Comparative Examples 2
Method by example 10 prepares modified polypropene, and different is not add any properties-correcting agent or thermoplastic elastomer, and the performance of gained modified polypropene sees Table 2.
Comparative Examples 3
Method by example 10 prepares modified polypropene, and different is that the properties-correcting agent that adds is M, and the performance of gained modified polypropene sees Table 2.
Comparative Examples 4
Method by example 10 prepares modified polypropene, and different is ethylene-octene copolymer (the POE)/high density polyethylene(HDPE) toughened master batch of properties-correcting agent for adopting the described method of patent CN01114932.9 to prepare that adds, and the performance of gained modified polypropene sees Table 2.
By table 2 data as can be known, the modified polypropene product of using properties-correcting agent preparation of the present invention is than Comparative Examples, and its normal temperature notched Izod impact strength significantly strengthens, and elongation at break also increases to some extent, illustrates that the toughness of product strengthens.And flexural strength and modulus in flexure are suitable with Comparative Examples 2, illustrate that the modified polypropene product that is made by properties-correcting agent of the present invention still has higher rigidity.
Table 1
Claims (12)
1, a kind of polyolefine toughening modifier comprises the cross-linking agent that contains following component of partial alcoholysis:
Ethylene-vinyl acetate copolymer 60～80 quality %
New LDPE (film grade) 20～40 quality %
The alcoholysis degree of described cross-linking agent is 80～90%, the melting index of described ethylene-vinyl acetate copolymer is 2～60 grams/10 minutes, wherein the content of vinyl acetate is 10～50 quality %, and the density of described new LDPE (film grade) is 0.91～0.93 gram per centimeter
3, melting index is 1～5 gram/10 minutes.
2, a kind of polyolefine toughening modifier comprises the cross-linking agent that contains following component of partial alcoholysis:
Ethylene-vinyl acetate copolymer 60～80 quality %
New LDPE (film grade) 18～35 quality %
Inorganics 1～15 quality %
The alcoholysis degree of described cross-linking agent is 80～90%, the melting index of described ethylene-vinyl acetate copolymer is 2～60 grams/10 minutes, wherein the content of vinyl acetate is 10～50 quality %, and the density of described new LDPE (film grade) is 0.91～0.93 gram per centimeter
3, melting index is 1～5 gram/10 minutes.
3,, it is characterized in that the degree of crosslinking before the described cross-linking agent alcoholysis is 30～50% according to claim 1 or 2 described properties-correcting agent.
4, according to claim 1 or 2 described properties-correcting agent, the melting index that it is characterized in that described ethylene-vinyl acetate copolymer is 5～10 grams/10 minutes, and wherein the content of vinyl acetate is 20～30 quality %.
5,, it is characterized in that described inorganics granularity is 0.01～5 micron according to the described properties-correcting agent of claim 2.
6,, it is characterized in that described inorganics is selected from talcum powder, barium sulfate, titanium dioxide, lime carbonate or white carbon black according to the described properties-correcting agent of claim 2.
7,, it is characterized in that described polyolefine is a polypropylene according to claim 1 or 2 described properties-correcting agent.
8, the preparation method of the described properties-correcting agent of a kind of claim 1 comprises the steps:
(1) premix: it is 50～100 rev/mins low speed mixer that ethylene-vinyl acetate copolymer, new LDPE (film grade) are added rotating speed successively, and 20～40 ℃ of pre-mixings slowly add linking agent again and mix;
(2) crosslinked: mixed material of (1) step is added the homodromy parallel twin screw extruder, and controlling each section extrusion temperature is 150～250 ℃, and screw speed is 150～250 rev/mins, and the feeding machine rotating speed is 20～50 rev/mins, obtains the cross-linking agent particle;
(3) partial alcoholysis: the cross-linking agent particle is added in the aqueous solution of the potassium hydroxide that contains 1.0～3.0 quality %, partial alcoholysis is carried out in 50～70 ℃ of reactions, and the control alcoholysis degree is 80～90%.
9, in accordance with the method for claim 8, when it is characterized in that (1) step, premix was reinforced, ethylene-vinyl acetate copolymer, new LDPE (film grade) and inorganics are added low speed mixer successively.
10, in accordance with the method for claim 9, it is characterized in that described inorganics is selected from talcum powder, barium sulfate, titanium dioxide, lime carbonate or white carbon black.
11,, it is characterized in that described linking agent is selected from ditertiary butyl peroxide or 2, the 5-2 according to claim 8 or 9 described methods.
12, in accordance with the method for claim 8, it is characterized in that the aqueous solution of used potassium hydroxide and the mass ratio of cross-linking agent are 2.1～14.0: 1, the alcoholysis time is 3～6 hours.
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| CN104448513A (en) * | 2014-10-28 | 2015-03-25 | 中国石油天然气集团公司 | Low-temperature resistant toughening modifier, outer protective material, thermal insulation pipe and preparation method |
| DE112019000516B4 (en) * | 2018-01-24 | 2023-05-17 | Nike Innovate C.V. | Sole structure for an article of footwear and article of footwear |
| CN111793315A (en) * | 2020-07-28 | 2020-10-20 | 泰州思睿新材料科技有限公司 | Polyolefin toughening modifier and preparation method thereof |
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| JPH05245987A (en) * | 1992-03-05 | 1993-09-24 | Nippon Unicar Co Ltd | Agricultural laminated film and production thereof |
| JPH10118174A (en) * | 1996-10-24 | 1998-05-12 | Sekisui Chem Co Ltd | First-aid adhesive plaster |
| CN1257090A (en) * | 1999-12-24 | 2000-06-21 | 中国科学院上海原子核研究所 | Radiation crosslinking 150 deg.C flame-retarded polyolefine thermal shrinkage material |
| CN1258692A (en) * | 1998-12-31 | 2000-07-05 | 中国科学院近代物理研究所 | Crosslinked halide-free fireproof composite polyolefine material and its preparation |
| KR20010018443A (en) * | 1999-08-19 | 2001-03-05 | 유현식 | Crosslinkable resin composition for rotational moulding with high performance and weatherability |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05245987A (en) * | 1992-03-05 | 1993-09-24 | Nippon Unicar Co Ltd | Agricultural laminated film and production thereof |
| JPH10118174A (en) * | 1996-10-24 | 1998-05-12 | Sekisui Chem Co Ltd | First-aid adhesive plaster |
| CN1258692A (en) * | 1998-12-31 | 2000-07-05 | 中国科学院近代物理研究所 | Crosslinked halide-free fireproof composite polyolefine material and its preparation |
| KR20010018443A (en) * | 1999-08-19 | 2001-03-05 | 유현식 | Crosslinkable resin composition for rotational moulding with high performance and weatherability |
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