CN1036973A - The recovery of the ethylene glycol terephthalate waste material of contaminated with chlorine-containing polymer - Google Patents
The recovery of the ethylene glycol terephthalate waste material of contaminated with chlorine-containing polymer Download PDFInfo
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- CN1036973A CN1036973A CN 88102080 CN88102080A CN1036973A CN 1036973 A CN1036973 A CN 1036973A CN 88102080 CN88102080 CN 88102080 CN 88102080 A CN88102080 A CN 88102080A CN 1036973 A CN1036973 A CN 1036973A
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Abstract
The ethylene glycol terephthalate waste material that the surface scribbles chlorine-containing polymer (as polyvinylidene chloride or polyvinyl chloride) can reclaim and utilization again by melt-blending process, and method is to make it and the ethylene copolymer blend that contains epoxy group(ing).It is identical with the PET raw material to melt the course of processing.The polymkeric substance that reclaims and reprocess has good physicals and barrier propterty.
Description
The present invention relates to scribble the recovery and the utilization again of the ethylene glycol terephthalate (PET) of chlorine-containing polymer, and the method for making goods with salvage material.
A large amount of pet wastes can utilize again for industry, for example exhausted PET bottle, fiber and film.But these waste materials are difficult to not treated direct use, because some films and bottle, owing to requiring stopping property to apply the chlorine-containing polymer thin layer to oxygen and water, commonly used vinylidene chloride homopolymer or vinylidene chloride and (about 0.1-10%(weight) on a small quantity arranged) multipolymer of other vinyl comonomer, the latter can be a chlorating, also can be not have the chlorating monomer.These additional comonomers can be according to producer's requirement, also often considers the requirement of film coated industry and changes.Coating also can adopt the multipolymer of polyvinyl chloride and vinyl chloride monomer and a small amount of other unsaturated monomer.Chlorine-containing polymer also can be coated on the photograph polyester film base and make tackiness agent in addition.When vinylidene chloride polymer was used making coatings, the amount of coating accounted for the 0.01-0.24%(weight of coated polymkeric substance total amount usually).But so not strict to making a gesture of measuring requirement, often regulate according to service requirements.The pet waste that scribbles chlorine-containing polymer can not use usually like this, must boil or polymeric coating is removed in other chemical treatment through NaOH.For example, vinylidene chloride polymer is lower than the processing temperature of normal PET about 200 ℃ of decomposition, sneaks into the pet waste that contains vinylidene chloride polymer because of carelessness as work in-process, will discharge HCL, and the result causes PET decomposition, variable color and equipment corrosion.Also there is not a kind of energy to remove chlorine-containing polymer earlier and the practical approach of this pet waste of melt-processed so far.
Therefore, apparent, invent a kind of recovery and utilize the method that the pet waste of millions of kilograms of amounts is arranged this every year again, will have very big industrial significance.
The method that the invention provides a kind of recovery of the polyethylene terephthalate waste material that scribbles chlorine-containing polymer and utilize again.Present method be with above-mentioned waste material with in the ethylene copolymer E/ of its weight 5-25% */Y is at 260-310 ℃ of following melt blending, wherein:
E is the group that is formed by ethene, and its amount accounts for the 40-99.5%(weight of ethylene copolymer);
* be by
The group that forms
Wherein: R
1Be that carbonatoms is the alkyl of 1-8,4-6 carbon atom preferably, most preferred is 4 carbon atoms;
R
2Be hydrogen, methyl or ethyl, preferentially select hydrogen and methyl for use, the most handy hydrogen;
* content be the 0-40%(weight of ethylene copolymer), preferentially select 15-35%(weight for use), the most handy 20-35%(weight);
Y is the copolymerisable monomer that contains epoxy group(ing), but but be selected from the diolefine of 4-12 the carbon atom that the vinyl of unsaturated organic acid epoxy ester compounds copolymerization of copolymerization or allyl group ether epoxy compound and single epoxy group(ing) replace, its amount is the 0.5-20%(weight of ethylene copolymer), preferentially select 2-10%(weight for use), be preferably 3-8%(weight).
Other common monomer also can exist on a small quantity as CO and methyl acrylate, as long as the physics and the mechanical property of not obvious change ethylene copolymer.To influence usefulness with the ethene polymers that is lower than lower limit, and be higher than the upper limit and will cause the system over-crosslinked.
Preferred comonomer Y is glycidyl methacrylate and glycidyl acrylate, preferred ethylene copolymer E/ */Y is the positive butyl ester of ethylene/acrylic acid/glycidyl methacrylate terpolymer.
The used ethylene copolymer of the inventive method can be by ethene, contain comonomer * (if any) that epoxy group(ing) monomer Y and front were said, at high temperature, high pressure with can produce direct polymerization in the presence of the initiator of free radical and obtain.Polymerization temperature is selected 100-270 ℃ for use, and the most handy 130-230 ℃, polymerization pressure is selected for use＞70MPa usually, the most handy 140-350MPa.
This analog copolymer and copolymerization process thereof are known or/and in English Patent 1,352,088(Sumit mo chemistry company limited) in existing narration.Except above-mentioned E/ */the Y multipolymer, blend polymer also can contain a spot of low modulus toughening polymer (accounting for 5～25%(weight of polymkeric substance total amount)).Suitable toughening polymer is at United States Patent (USP) 4,172,859(Epstein) in existing narration, this paper incorporates this case into reference to this patent and with it.Typically increasing polymkeric substance can be as following replacing or random copolymers: ethylene/acrylic acid isobutyl ester/methacrylic acid ter-polymer; Ethylene/methyl acrylate/ethyl maleate terpolymer and rush down-100% salt through zinc, beer ⒏ beer ⑻ piperazine figure Dao; And ethylene/vinyl acetate 1-carbonoxide terpolymer.
The pet waste that scribbles vinylidene chloride polymer and similar chlorine-containing polymer is a kind of thermoplastic material, and is the same with PET resin raw material, can descend with blend at about 270-310 ℃, extrude or injecting method processing.Certainly, can be used to pet waste from industrial level PET resin.The blend of waste material can be carried out in any suitable full scale plant, as forcing machine or blending machine, but preferentially selects forcing machine for use, and its barrel zone temperature remains on about 260-310 ℃, promptly processes under the melt temperature of polymer materials.
Be very unexpectedly, when these scribble the pet waste of chlorine-containing polymer and above-mentioned E/ */during (forcing machine or injector) blend, the corrosion of the degraded of polymkeric substance and/or decolouring and equipment greatly reduces the Y ethylene copolymer in polymer melt processing units commonly used.The goods that obtain all have acceptable mechanical property for many application, and have the good barrier propterty of PET inherent, therefore industrial application value are arranged, for example various types of containers, especially solvent type canister, and PET film.
Further discover, when adding waste material amount 0.05-1.0%(weight) another kind of additive such as lime carbonate, calcium stearate, another kind of metallic stearate or hydrogenation talcite (or claiming hydrogenation damourite) in E/ */the Y multipolymer in the time, have also that significantly other improve effect.Those other metallic stearates can be used in any one metallic stearate that often can buy on the market, or are used in Zinic stearas, aluminum stearate, sodium stearate, potassium stearate of lubricant, soap and other similar aspect etc.The hydrogenation talcite is a kind of natural mineral, and its molecular formula is Mg
6Al
2(OH)
13CO
34H
2O is except the natural hydrogenated talc lump also can use the slightly different synthetic product Mg of molecular formula in an identical manner
45Al
2(OH)
13CO
3 3.5H
2O substitutes.This synthetics can have been bought by kgowa chemistry company limited (Japan, Osaka), and commodity are called DHT-4A.In case of necessity can be with natural or synthetics roasting, to remove its crystal water.
The present invention now is illustrated with following specific examples, and the composition in interior, ratio be percentage meter by weight all, except as otherwise noted.
Example 1
Pet waste is that its limiting viscosity is about 0.58(and measures in phenol/tetrachloroethane mixed solvent of 60: 40 through the film of orientation and heat setting type).Wherein the part film scribbles metachloroethylene copolymer, and its amount accounts for the 320PPm of waste material by cl content.
Film is cut into pieces,, is extruded, the mouth mould that material is extruded into bar is housed in the machine with werner and Pfleiderer twin screw extruder with second kind of polymer blending, after again bar is cut into particle so that further processing.Forcing machine is equipped with venting port.About 280 ℃ of the melt temperature of polymkeric substance is expelled to the pellet of making in the mould that the mould temperature is about 40 ℃, makes sample cup or tension test batten, and the sample cup is high 94 millimeters, and base diameter is 56 millimeters, and 70 millimeters of top diameters, sidewall and base thickness are 1.6 millimeters.Thick 1/8 inch of standard-sized tension test batten (3.2 millimeters) is pressed ASTMD 256 standard tests.
With the another kind of polymkeric substance of pet waste blend be the positive butyl ester/glycidyl methacrylate of ethylene/acrylic acid (67: 28: 5) multipolymer (tube claims EBAGMA) or ethylene/propylene n-butyl acrylate (74: 26) multipolymer (tube claims EBA), the latter does not belong to the scope of the invention.Its toughness is surveyed with shock-testing machine (improved Gardner shock-testing machine) in the bottom of the sample cup that injection molding obtains, striking energy can reach 40 joules, with a diameter is that 1.25 centimetres striker pin is gone into bar, and the radius of its top umbilical point is 6 millimeters.Damage penetrates sample with knocker and is as the criterion, the striking energy that the striking energy that test needs can reach less than instrument, and it the results are shown in following table:
In the test of this class, when impact value during greater than erg-ten, toughness belongs to and can accept, but will remember that preferred embodiment of the present invention is under reduced pressure to operate, the venting port of forcing machine and vacuum, rather than link to each other with atmosphere.Can obtain higher impact value with this understanding, this moment, the erg-ten value was not good.In this example, handle the useless reclaimed materials of the PET that contains vinylidene chloride with 5-25%EBAGMA and obtained satisfied toughness, then not good during with 5-25%EBA.The pet waste of coated does not all get satisfactory result two kinds of situations.
Example 2
In another group test, the test batten is made under the following conditions: extrusion was stablized about 15 minutes, and the gas that comes out from the forcing machine venting port is by two absorption cold-traps that contain 0.1NNaOH, and evolving gas is all by cold-trap bubbling 25 minutes.
The cl content of liquid in the later chromatograph cold-trap.
In the battery of tests by scope of the invention operation, with 20%EBAGMA and the pet waste blend that contains vinylidene chloride polymer.In contrast, same waste material is with same ratio and EBA blend.Cl content in the pet waste all is 660PPm in both cases.Test-results is listed in the table below:
A large amount of minimizings of effusion chlorine and toughness raising have shown the usefulness of EBAGMA in stabilising system.
Example 3
Except that the forcing machine venting port link to each other with vacuum and under the vacuum of 10kpa the operation, other operational condition is with example 1.In first group of test, not doping in pet waste and the EBAGBA blend.In second group of test, add a small amount of calcium stearate (technical grade, Fisher scientific company product).The a small amount of DHT-4A(kyowa chemical industry of interpolation company limited in the 3rd group).In all each groups, the amount of vinylidene chloride polymer is 320ppm by cl content in the pet waste, and test-results is listed in the table below:
(a) calcium stearate
(b) synthesizing hydrogenated talcite
By above-mentioned data as seen, even exist under the situation additive-free, granulation is under reduced pressure compared with exhaust under atmospheric pressure (referring to example 1), can obtain obviously high shock strength (seeing example 1).Add calcium stearate or hydrogenation talcite in blend, the improvement of impact property is more obvious.
Claims (33)
1, a kind of method that reclaims and utilize the polyethylene terephthalate waste material that scribbles chlorine-containing polymer again, described method comprises mixes above-mentioned waste material mutually with the ethylene copolymer E/X/Y that is equivalent to its amount 5-25% (weight), and under 260-310 ℃ melt temperature with above-mentioned polymer composition melt blending, wherein:
E is the group that is formed by ethene, and its amount accounts for the 40-99.5% (weight) of ethylene copolymer;
X be by
The group that forms
Wherein: R
1Be that carbonatoms is the alkyl of 1-8;
R
2Be hydrogen, methyl or ethyl;
The content of X accounts for the 0-40% (weight) of ethylene copolymer;
Y is the copolymerisable monomer that contains epoxy group(ing), but is selected from the unsaturated organic acid epoxy ester compounds of copolymerization, but has the diolefine of 4-12 carbon atom of copolymerizable vinyl groups or allylic ether epoxy compound and the replacement of single epoxy group(ing); Its amount accounts for the 0.5-20% (weight) of ethylene copolymer.
2, according to the process of claim 1 wherein R
1Contain 4-6 carbon atom.
3, according to the method for claim 2, R wherein
1Contain 4 carbon atoms.
4, according to the process of claim 1 wherein that Y is selected from glycidyl acrylate and glycidyl methacrylate.
5, according to the method for claim 4, the therein ethylene multipolymer is the multipolymer of ethene, n-butyl acrylate and glycidyl methacrylate.
6, according to the process of claim 1 wherein R
2Be hydrogen or methyl.
7, according to the process of claim 1 wherein R
2Be hydrogen.
8, according to the process of claim 1 wherein * account for the 15-35%(weight of ethylene copolymer).
9, according to the method for claim 8, wherein * account for the 20-35%(weight of ethylene copolymer).
10, do not contain monomer X according to the process of claim 1 wherein.
11, according to the process of claim 1 wherein that Y accounts for the 2-10%(weight of ethylene copolymer).
12, according to the method for claim 11, wherein Y accounts for the 3-8%(weight of ethylene copolymer).
13, account for the additive that is equivalent to waste material weight 0.05-1.0% according to the process of claim 1 wherein that blend also contains, additive can be by selecting for use in lime carbonate, calcium stearate, other Metallic stearates, the natural and synthesizing hydrogenated talcite.
14, according to the process of claim 1 wherein that blend also contains the low modulus toughening polymer that is equivalent to total polymer weight 5-25%.
15, a kind of polymer blend compositions, it mainly is made up of ethylene glycol terephthalate waste material that scribbles chlorine-containing polymer and the ethylene copolymer E/X/Y melt blending that is equivalent to its weight 5-25%, wherein:
E is the group that is formed by ethene, and its amount accounts for the 40-99.5%(weight of ethylene copolymer);
* be by
The group that forms
Wherein: R
1Be that carbonatoms is the alkyl of 1-8;
R
2Be hydrogen, methyl or ethyl;
* content account for the 0-40%(weight of ethylenic copolymer).
Y is the copolymerisable monomer that contains epoxy group(ing), but but be selected from copolymerization the unsaturated organic acid epoxy ester compounds, have the diolefine of 4-12 the carbon atom that copolymerizable vinyl groups or allylic ether epoxy compound and single epoxy group(ing) replace; Its amount accounts for the 0.5-20%(weight of ethylene copolymer).
16, according to the composition of claim 15, R wherein
1Contain 4-6 carbon atom.
17, according to the composition of claim 16, R wherein
1Contain 4 carbon atoms.
18, according to the composition of claim 15, wherein Y is selected from glycidyl acrylate and glycidyl methacrylate.
19, according to the composition of claim 17, the therein ethylene multipolymer is the multipolymer of ethene, n-butyl acrylate and glycidyl methacrylate.
20, according to the composition of claim 15, R wherein
2Be hydrogen or methyl.
21, according to the composition of claim 20, R wherein
2Be hydrogen.
22, according to the composition of claim 15, wherein * account for the 15-35%(weight of ethylene copolymer).
23, according to the composition of claim 22, wherein * account for the 20-35%(weight of ethylene copolymer).
24, according to the composition of claim 15, wherein do not contain monomer X.
25, according to the composition of claim 15, wherein Y accounts for the 2-10%(weight of ethylene copolymer).
26 gather the composition of cane ɡ 5, and wherein Y accounts for the 3-8%(weight of ethylene copolymer).
27, according to the composition of claim 15, wherein also contain the additive that is equivalent to waste material weight 0.05-1.0%, additive can be selected for use from lime carbonate, calcium stearate, other Metallic stearates, natural and synthesizing hydrogenated talcite.
28, according to the composition of claim 15, wherein blend also contains the low modulus toughening polymer that accounts for total polymer weight 5-25%.
29, the goods that obtain of the composition by melt-processed claim 15.
30, the goods that obtain of the composition by melt-processed claim 19
31, the goods according to claim 29 are container and film.
32, the goods according to claim 19 are container and film.
33, the goods according to claim 32 are paint jars.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102080 CN1036973A (en) | 1986-12-30 | 1988-04-14 | The recovery of the ethylene glycol terephthalate waste material of contaminated with chlorine-containing polymer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/947,835 US4826897A (en) | 1986-12-30 | 1986-12-30 | Process for reclaiming polyethylene terephalate scrap contaminated with chlorine-containing polymer |
| CN 88102080 CN1036973A (en) | 1986-12-30 | 1988-04-14 | The recovery of the ethylene glycol terephthalate waste material of contaminated with chlorine-containing polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1036973A true CN1036973A (en) | 1989-11-08 |
Family
ID=25742432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88102080 Pending CN1036973A (en) | 1986-12-30 | 1988-04-14 | The recovery of the ethylene glycol terephthalate waste material of contaminated with chlorine-containing polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1036973A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795092A (en) * | 2014-10-03 | 2017-05-31 | Dic株式会社 | Epoxy ester compounds, cellulose ester resin composition, optical thin film and liquid crystal display device |
-
1988
- 1988-04-14 CN CN 88102080 patent/CN1036973A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795092A (en) * | 2014-10-03 | 2017-05-31 | Dic株式会社 | Epoxy ester compounds, cellulose ester resin composition, optical thin film and liquid crystal display device |
| CN106795092B (en) * | 2014-10-03 | 2019-05-17 | Dic株式会社 | Epoxy ester compounds, cellulose ester resin composition, optical thin film and liquid crystal display device |
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|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |