WO2017165746A1 - Enhanced melt strength thermoplastic formulation - Google Patents
Enhanced melt strength thermoplastic formulation Download PDFInfo
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- WO2017165746A1 WO2017165746A1 PCT/US2017/023986 US2017023986W WO2017165746A1 WO 2017165746 A1 WO2017165746 A1 WO 2017165746A1 US 2017023986 W US2017023986 W US 2017023986W WO 2017165746 A1 WO2017165746 A1 WO 2017165746A1
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- melt strength
- formulation
- high melt
- thermoplastic
- molecular weight
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C08F2/00—Processes of polymerisation
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
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- C08L67/06—Unsaturated polyesters
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Definitions
- the invention relates to a thermoplastic formulation having a thermoplastic matrix and 1- 40 percent by weight of a high molecular weight thermoplastic processing aid, with a weight average molecular weight of greater than 100,000 g/mol.
- the formulation has a high melt strength, yet is processable under typical melt processing conditions.
- the formulation is useful for melt-processed products, including extruded products such as extruded sheet, foam, co- extruded profiles, blown films, and other objects typically formed by a heat processing operation.
- Thermoplastics are highly versatile polymers which are easily melt-processed into many different shapes, such as profiles, sheets, rods; molded and blow molded into films and objects; and extruded or co-extruded over many other thermoplastic substrates.
- melt strength of a thermoplastic polymer formulation is a key factor in the success of many melt-process operations.
- higher melt strength prevents uncontrolled expansion of the foam cells, to provide a small, uniform cell size.
- Higher melt strength also prevents a foam from collapsing prior to cooling, and locks in the foam structure.
- the high melt strength allows the pulling of a hot, extruded solid or foamed material through sizing or calibrating equipment.
- high melt strength provides the polymer melt with integrity, so a continuous material is formed without gaps.
- melt strength of a polymer formulation is to increase the average molecular weight of the polymer. While this approach results in a high melt strength, the melt viscosity can quickly increase to the point that the melt is too thick to process in typical melt processing equipment. Higher melt strength is also known to result from the presence of the higher degree of long chain branching and network/cross -linked structures that can be found in the very high molecular weight process aids. Long chain branching can be introduced in polymers via irradiation or by modification of the polymerization process.
- Melt processing aids which are high molecular weight compatible polymers, have been used in the PVC industry (US 2009/0093560) to increase the melt strength of a PVC formulation.
- thermoplastic formulation having a low enough melt viscosity that allows for processing under typical melt-processing conditions.
- thermoplastic processing aids can be added to a thermoplastic matrix to significantly increase the melt strength of the thermoplastic formulation, with little or no increase in melt viscosity - allowing the high melt strength formulation to be melt processed in typical equipment under typical conditions.
- the high molecular weight acrylic processing aids have a molecular weight of greater than 100,000 g/mol.
- the thermoplastic formulation, in which the processing aid can be used at lower levels, has a minimal effect on mechanical properties such as modulus and hardness in articles made with Applicant's formulation. Due to the low use levels and the shear thinning behavior of the high molecular weight process aid with high polydispersity, the viscosity at typical processing conditions can be minimally affected.
- the invention relates to a high melt strength thermoplastic formulation comprising: a) a thermoplastic matrix comprising a thermoplastic polymer;
- the invention further relates to a high strength thermoplastic formulation in which the matrix may optionally be impact-modified.
- the invention further relates to articles that are made from the high impact strength thermoplastic formulation, and also to melt processes for forming those articles.
- Figure 1 shows the melt strength curves of the pure thermoplastic matrix and the compound including 4% of an acrylic processing aid of Example 2.
- the invention relates to a thermoplastic formulation having a high melt strength, yet where the formulation is processable under typical melt-processing conditions.
- the formulation contains 1-40 weight percent, preferably from 3 to 25 weight percent, and most preferably from 5 to 15 weight percent, of a high molecular weight acrylic polymer process aid, and a matrix thermoplastic polymer, that is optionally impact modified.
- Copolymer is used to mean a polymer having two or more different monomer units.
- Polymer is used to mean both homopolymer and copolymers. Polymers may be straight chain, branched, star comb, block, or any other structure. The polymers may be homogeneous, heterogeneous, and may have a gradient distribution of co-monomer units. All references cited are incorporated herein by reference. As used herein, unless otherwise described, percent shall mean weight percent. Molecular weight is a weight average molecular weight as measured by GPC. In cases where the polymer contains some cross -linking, and GPC cannot be applied due to an insoluble polymer fraction, soluble fraction/ gel fraction or soluble faction molecular weight after extraction from gel is use. Acrylic Process Aid
- the acrylic polymer process aids of the invention are high molecular weight acrylic polymers.
- Other polymers miscible with polymethyl methacrylate may also be used in conjunction with the high molecular weight acrylic polymer, including but not limited to polylactic acid and polyvinylidne fluoride.
- high molecular weight is meant that the polymers have a weight average molecular weight of greater than 100,000 g/mol, preferably greater than 500,000 g/mol, more preferably greater than 1 million g/mol, and more preferably greater than 5 million g/mol.
- Acrylic polymers having a weight average molecular weight of 8 million g/mol or greater are also contemplated by the invention.
- the acrylic process aid preferably contains at least 50 weight percent of methyl methacrylate monomer units, and optionally comonomers, up to 50 weight percent.
- the methyl methacrylate monomer units make up from greater than 50 to 100 percent of the monomer mixture, preferably from 70 to 100 weight percent, and more preferably from 80 to 100 weight percent. 0 to less than 50 weight percent of other acrylate and methacrylate monomers or other ethylenically unsaturated monomers, included but not limited to, styrene, alpha methyl styrene, acrylonitrile, and crosslinkers at low levels may also be present in the monomer mixture.
- Suitable acrylate and methacrylate comonomers include, but are not limited to, methyl acrylate, ethyl acrylate and ethyl methacrylate, butyl acrylate and butyl methacrylate, iso-octyl methacrylate and iso-octyl acrylate, lauryl acrylate and lauryl methacrylate, stearyl acrylate and stearyl methacrylate, isobornyl acrylate and isobornyl methacrylate, methoxy ethyl acrylate and methoxy methacrylate, 2-ethoxy ethyl acrylate and 2-ethoxy ethyl methacrylate, and
- acrylic acids such as methacrylic acid and acrylic acid can be useful for the monomer mixture.
- other functionality can be added to the high molecular weight acrylic process aid through functional comonomers, including epoxy (such as glycidyl methacrylate), hydroxyl, and anhydride functional groups.
- Functional monomer units can be present at up to 70 weight percent of the acrylic polymer, preferably up to 50 weight percent.
- the acrylic polymer is a copolymer having 70 - 99.5 weight percent and more preferably 80 to 99 percent of methyl methacrylate units and from 0.5 to 30 weight percent of one or more C 1-8 straight or branched alkyl acrylate units.
- the polydispersity index of the high molecular weight acrylic process aid is in the range of 1.5 to 50, preferably from 2 to 40, and most preferably from 3 to 30.
- the high molecular weight acrylic process aid has a Tg of from -60 to 140°C, preferably from 0 to 120°C.
- the acrylic polymer can be an alloy with one or more compatible polymers, including ASA, PVDF and PLA.
- Preferred alloys are PMMA/polyvinylidene fluoride (PVDF) alloys, and PMMA/polylactic acid (PLA) alloys.
- the alloy contains 20 to 99 weight percent, preferably 50 to 95 weight percent, and more preferably 60-90 weight percent of the thermoplastic matrix, and 5 to 40 weight percent, preferably 10 to 30 weight percent of the compatible polymer.
- the high molecular weight acrylic process aid can be formed by any known polymerization process, such as emulsion, suspension, solution and reverse emulsion
- emulsion polymerization is the preferred process for producing the high molecular weight acrylic polymer.
- the polymer matrix of the invention is a thermoplastic, and preferably a thermoplastic that is compatible with the high molecular weight acrylic process aid.
- compatible as used herein, means that the polymers can be homogeneously mixed in the melt, without phase separation on a macro level.
- Useful matrix thermoplastic polymers include, but are not limited to, styrenic -based polymers, polyesters, polycarbonate, polyvinylidene fluoride, and
- thermoplastic polyurethane TPU
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PET-co-PEN glycol-modified polyethylene terephthalate
- PC polycarbonate
- ASA acrylonitrile-styrene-acrylate
- HIPS high-impact polystyrene
- PEEK polyether ether ketone
- PEKK polyether ketone
- ABS acrylonitrile-butadiene- styrene copolymers
- acrylic and polyvinyl chloride matrices are not included in the invention.
- the thermoplastic polymer can be an alloy with one or more compatible polymers, including but not limited to, ASA, PVDF and PLA.
- the alloy contains 2 to 95 weight percent, preferably 5 to 90 weight percent, and more preferably 20-80 weight percent of the thermoplastic homopolymer or copolymer, and 5 to 98 weight percent, preferably 10 to 95 weight percent and more preferably 20 to 80 weight percent of the compatible polymer.
- the thermoplastic polymer matrix may contain additives, including impact modifiers, and other additives typically present in polymer formulations, including but not limited to, stabilizers, plasticizers, fillers, coloring agents, pigments, dyes, antioxidants, antistatic agents, surfactants, toner, refractive index matching additives, matting agents, cross-linked polymer beads, additives with specific light diffraction, light absorbing, or light reflection characteristics, and dispersing aids.
- an additive is provided to help prevent degradation of the composition upon exposure to radiation, such as high levels of UV radiation or gamma radiation.
- Useful radiation stabilizers include, but are not limited to poly(ethylene glycol), poly(propylene glycol), butyl lactate, and carboxylic acids such as lactic acid, oxalic acid, acetic acid, or a mixture thereof.
- a chemical blowing agent such as monosodium citrate may be incorporated directly into the thermoplastic formulation, especially in a compounding step below the activation temperature of the blowing agent, or dry blended into the formulation immediately before foam extrusion.
- Useful impact modifiers include block copolymers, graft copolymers, and core/shell impact modifiers that are refractive-index matched to the matrix polymer.
- the impact modifier comprises at least 50 weight percent of acrylic monomer units.
- the impact modifier may be present at a level of from 0 to 80 weight percent, preferably 5 to 45, and more preferably from 10 to 30 weight percent, based on the total layer of matrix polymer and all additives. The level of impact modifier can be adjusted to meet the toughness needs for the end use of the composition.
- Core-shell impact modifiers are multi-stage, sequentially-produced polymer having a core/shell particle structure of at least two layers.
- the core- shell impact modifier has a soft (elastomeric) core, and a hard shell (greater than a Tg of 20°C).
- the core- shell modifier comprises three layers made of a hard core layer, one or more intermediate elastomeric layers, and a hard shell layer.
- the impact modifier is a core-shell structure, in which the shell contains at least 50 weight percent of methyl methacrylate monomer units.
- the core-shell impact modifier has a hard core (with a Tg greater than 30°C, and more preferably greater than 50°C).
- the core-shell impact modifier is made entirely of acrylic monomer units. Processing
- thermoplastic matrix polymer high molecular weight acrylic processing aid, and optional impact modifiers and other additives are blended in the melt.
- Two or more of the components of the thermoplastic formulation may first be dry blended, then melt blended.
- the high molecular weight acrylic polymer, thermoplastic matrix polymer and optionally impact modifier are melt blended together and formed into pellets. The pellets are then added with other components, such as dyes, fillers, and blowing agents at the melt processer operation.
- heat compounding can be accomplished by typical twin screw extrusion into a thermoplastic formulation.
- Single screw extruders, and extruders of other designs are also contemplated by the invention.
- emulsions of one or more of the high molecular weight process aid, matrix polymer and/or impact modifier can be blended as liquid dispersions, and the blend can be dried, such as by spray drying, coagulation, or freeze drying, to form a powder blend.
- the powder blend can then be further compounded with other components of the thermoplastic formulation either by dry blending or melt blending. Powder-powder blending is contemplated.
- An intermediate step, in which the spray-dried powder(s) are extrusion melt compounded into pellets for further melt compounding is also contemplated.
- Typical melt processing operations in which the high melt strength thermoplastic formulation of the invention having a manageable melt viscosity may be useful include, but are not limited to, extrusion, co-extrusion, injection molding, compression molding, film extrusion, and blow molding operations.
- the high molecular weight, high polydispersity formulation of the invention undergoes significant shear thinning, so its effect on high shear viscosity will be minimal.
- Process aids of the invention having higher levels of long chain branching can more effectively increase the melt strength.
- thermoplastic formulations of the invention are useful in melt-processing
- a high melt strength formulation provides several advantages in a foaming operation.
- the high melt strength provides control over the expansion of the individual cells, allowing for a more uniform cell size, and smaller cell size. Die swell of the foam is also better controlled.
- the high melt strength also helps to prevent the collapse of the cells, once formed. Further, the extruded foam can be more easily sized and/or calendared without deforming the foamed article, due to the higher melt strength of the polymer
- higher melt strength acrylic provides more continuity in the thermoplastic formulation, leading to little or no gaps or pit marks in the thermoplastic layer, and further there is an increase in die swell to better match the coextruded substrate.
- Higher melt viscosity of an extruded thermoplastic decreases the amount of sag for rods, sheets, and other articles upon leaving the die, and also less sagging for thermoplastic layers in a co-extrusion.
- the line was rinsed with 50 g of water.
- the reaction mixture was left to rise in temperature to the exothermal peak.
- the polymerization was then left to completion for 60 minutes after the exothermal peak.
- the reactor was cooled down to 30 degrees centigrade and the latex removed.
- the latex is dried by spray drying.
- the molecular weight of the acrylic processing aid described in this example was about 6 million g/mol.
- Another processing aid with specific anti-sticking composition such, as the one described in the patent EP 0367 198 B l could also be used in the process.
- the two processing aids would be co-spray dried using 10 wt. % of the anti-sticking processing aid and 90 wt. % of the processing aid described by the preparation earlier in this example.
- Co-spray drying as used in this example consists of blending the two acrylic processing aid latexes and then isolating the blend by spray drying. This results in a final powder particle or grain comprised of both processing aids.
- ASA acrylonitrile-styrene-acrylate copolymer
- the ASA formulation is melt compounded in a twin screw extruder in order to homogenize the thermoplastic matrix and processing aids.
- the ASA formulation should have both high melt strength and improved anti-sticking (better metal release).
- Acrylic Processing Aid Preparation Charged into a reactor, with stirring, were 8600 g of water, 5.23 g of Na 2 C03 and 38.20 g of sodium lauryl sulfate, and the mixture was stirred until complete dissolution. Three vacuum- nitrogen purges were carried out in succession and the reactor left under a slight vacuum. The reactor was then heated. At the same time, a mixture comprising 4687.2 g of methyl methacrylate and 520.8 g of n-butyl acrylate was nitrogen-degassed for 30 minutes. Next, the mixture was rapidly introduced into the reactor using a pump. When the temperature of the reaction mixture reached 55 degrees centigrade, 7.81 g of potassium persulfate dissolved in 98.08 g of water were introduced.
- the line was rinsed with 50 g of water.
- the reaction mixture was left to rise in temperature to the exothermal peak.
- the polymerization was then left to completion for 60 minutes after the exothermal peak.
- the reactor was cooled down to 30 degrees centigrade and the latex removed.
- the latex is dried by spray drying.
- the molecular weight of the acrylic processing aid described in this example was about 6 million g/mol.
- a standard, commercial segmented block copolymer consisting of successive hard or rigid blocks and soft or flexible segments was used.
- a copolymer with polyamide rigid blocks and polyether soft blocks was used.
- melt strength curves of the pure thermoplastic matrix and the compounded thermoplastic formulation including 4% of an acrylic processing aid are shown in Figure 1. Melt strength and stress ratio are reported in Table 1.
- the compound including 4% of an acrylic processing aid shows an increase from 30 to 40% from the thermoplastic matrix.
- the thermoplastic formulation including 4% of an acrylic processing aid also reported better melt extension at low acceleration conditions (Table 2).
- a high melt strength thermoplastic formulation comprising: a) a thermoplastic matrix comprising at least one thermoplastic polymer; b) 1 to 40 weight percent of a high molecular weight acrylic process aid, wherein said high molecular weight acrylic process aid has a molecular weight or greater than 100,000 g/mol.
- thermoplastic matrix is selected from the group consisting of styrenic-based polymers, polyesters, polycarbonate, polyvinylidene fluoride, and thermoplastic polyurethane (TPU), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), PET-co-PEN, glycol-modified
- PETG polyethylene terephthalate
- PET-co-PETG polycarbonate
- ASA acrylonitrile-styrene- acrylate
- HIPS high-impact polystyrene
- PEEK polyether ether ketone
- PEKK polyether ketone ketone
- ABS acrylonitrile-butadiene-styrene
- thermoplastic formulation of any of aspects 1 or 2, wherein said acrylic process aid has a molecular weight of greater than 500 g/mol, preferably greater than 1 million g/mol, more preferably greater than 5 million g/mol, and more preferably greater than 8 million g/mol.
- thermoplastic formulation of any of aspects 1 to 3, wherein said acrylic process aid comprises 50 to 100 weight percent of methyl methacrylate monomer units, and from 0 to 50 weight percent of one or more monomer units selected from the group consisting of (meth)acrylates, styrene, alpha methyl styrene, acrylonitrile, glycidyl methacrylate, and
- thermoplastic formulation of any of aspects 1 to 5 wherein said acrylic process aid is formed by an emulsion polymer process.
- said thermoplastic matrix further comprises from 2 to 95 weight percent of one or more compatible polymers, based on the weight of the polymers in the thermoplastic matrix.
- thermoplastic matrix further comprises from 5 to 60 weight percent of one or more impact modifiers.
- said impact modifiers are core-shell impact modifiers having a shell comprising methyl methacrylate monomer units, and a soft core with a Tg of less than -20°C.
- thermoplastic polymer matrix further comprises at least one additive selected from the group consisting of stabilizers, plasticizers, fillers, coloring agents, pigments, dyes, antioxidants, antistatic agents, surfactants, toner, refractive index matching additives, matting agents, cross- linked polymer beads, additives with specific light diffraction, light absorbing, or light reflection characteristics, and dispersing aids.
- said high molecular weight process aid has a polydispersity index of from 1.5, preferably from 2 to 40, and most preferably from 3 to 30.
- said article is a sheet, film, rod, profile, or co-extruded sheet, film, profile, or co-extruded capstock over a substrate, and may be solid or a foam.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX2018011380A MX2018011380A (es) | 2016-03-25 | 2017-03-24 | Formulacion termoplastica mejorada de resistencia a la fundicion. |
| EP17771222.1A EP3433290A4 (en) | 2016-03-25 | 2017-03-24 | THERMOPLASTIC FORMULATION WITH IMPROVED MELTING THICKNESS |
| US16/086,018 US20200291214A1 (en) | 2016-03-25 | 2017-03-24 | Enhanced melt strength thermoplastic formulation |
| JP2018550373A JP2019509390A (ja) | 2016-03-25 | 2017-03-24 | 高溶融強さ熱可塑性物質配合物 |
| CN201780018609.3A CN109071717A (zh) | 2016-03-25 | 2017-03-24 | 具有提高的熔体强度的热塑性配制物 |
| KR1020187031006A KR20180128034A (ko) | 2016-03-25 | 2017-03-24 | 향상된 용융 강도의 써모플라스틱 제형 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662313284P | 2016-03-25 | 2016-03-25 | |
| US62/313,284 | 2016-03-25 |
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| WO2017165746A1 true WO2017165746A1 (en) | 2017-09-28 |
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ID=59900786
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2017/023986 Ceased WO2017165746A1 (en) | 2016-03-25 | 2017-03-24 | Enhanced melt strength thermoplastic formulation |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20200291214A1 (enExample) |
| EP (1) | EP3433290A4 (enExample) |
| JP (1) | JP2019509390A (enExample) |
| KR (1) | KR20180128034A (enExample) |
| CN (1) | CN109071717A (enExample) |
| MX (1) | MX2018011380A (enExample) |
| WO (1) | WO2017165746A1 (enExample) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401228A (zh) * | 2018-11-07 | 2019-03-01 | 长沙浩然医疗科技有限公司 | 一种塑料添加剂及生产工艺 |
| CN111792381A (zh) * | 2020-07-13 | 2020-10-20 | 上海耐默光电技术有限公司 | 一种低摩擦阻力耐高温耐磨的风动送样盒及其制备方法 |
| CN114369213A (zh) * | 2022-01-14 | 2022-04-19 | 河北明润复合材料科技有限公司 | Pet增粘剂、pet发泡材料及其制备方法 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7233378B2 (ja) * | 2017-04-25 | 2023-03-06 | ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー | ポリ(エーテルエーテルケトン)ポリマー成分を用いた3次元物体の製造方法 |
| US11306191B2 (en) * | 2018-09-17 | 2022-04-19 | Cpg International Llc | Polymer-based construction materials |
| KR102139014B1 (ko) * | 2019-11-27 | 2020-07-28 | 다이텍연구원 | 내구성 및 경량성이 우수한 자전거 프레임용 복합수지 성형재의 제조방법 및 이에 의해 제조되는 복합수지 성형재 |
| CN112625408B (zh) * | 2020-12-18 | 2022-05-17 | 浙江巨化新材料研究院有限公司 | 一种韧性的pet闭孔发泡材料及其制备方法 |
| CN113402678B (zh) * | 2021-06-17 | 2022-04-22 | 华南理工大学 | 一种两步反应制备高熔体强度聚乳酸树脂的方法 |
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- 2017-03-24 CN CN201780018609.3A patent/CN109071717A/zh active Pending
- 2017-03-24 US US16/086,018 patent/US20200291214A1/en not_active Abandoned
- 2017-03-24 EP EP17771222.1A patent/EP3433290A4/en not_active Withdrawn
- 2017-03-24 MX MX2018011380A patent/MX2018011380A/es unknown
- 2017-03-24 KR KR1020187031006A patent/KR20180128034A/ko not_active Ceased
- 2017-03-24 WO PCT/US2017/023986 patent/WO2017165746A1/en not_active Ceased
- 2017-03-24 JP JP2018550373A patent/JP2019509390A/ja active Pending
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| US20100048797A1 (en) * | 2006-07-21 | 2010-02-25 | Arkema France | Thermoplastic compositions having improved properties during and after processing steps, process for manufacturing an article and article thus obtained |
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| CN111792381A (zh) * | 2020-07-13 | 2020-10-20 | 上海耐默光电技术有限公司 | 一种低摩擦阻力耐高温耐磨的风动送样盒及其制备方法 |
| CN114369213A (zh) * | 2022-01-14 | 2022-04-19 | 河北明润复合材料科技有限公司 | Pet增粘剂、pet发泡材料及其制备方法 |
| CN114369213B (zh) * | 2022-01-14 | 2023-07-14 | 河北明润复合材料科技有限公司 | Pet增粘剂、pet发泡材料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019509390A (ja) | 2019-04-04 |
| EP3433290A4 (en) | 2019-10-30 |
| MX2018011380A (es) | 2019-07-04 |
| EP3433290A1 (en) | 2019-01-30 |
| CN109071717A (zh) | 2018-12-21 |
| KR20180128034A (ko) | 2018-11-30 |
| US20200291214A1 (en) | 2020-09-17 |
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