CN1498918A - Processing modifying agent for PVC and preparing technique method - Google Patents
Processing modifying agent for PVC and preparing technique method Download PDFInfo
- Publication number
- CN1498918A CN1498918A CNA021350930A CN02135093A CN1498918A CN 1498918 A CN1498918 A CN 1498918A CN A021350930 A CNA021350930 A CN A021350930A CN 02135093 A CN02135093 A CN 02135093A CN 1498918 A CN1498918 A CN 1498918A
- Authority
- CN
- China
- Prior art keywords
- acid
- pvc
- modifier
- derivative
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A processing modifier for PVC is prepared through polycondensating reaction between organic acid and/or its derivative and polyol at 200-300 deg.C for 0.5-2.0 hr to obtain A, polycondensating reaction with one or more kinds of polyol to obtain B, and polycondensating reaction between A and/or B, organic acid and/or its derivative, and light RE oxide at 100-200 deg.C for 0.5-5 hr. Its advantages are high utilization rate of equipment, less energy consumption and no environmental pollution.
Description
[technical field]
The present invention relates to a kind of properties-correcting agent of synthetic resins, more particularly, the present invention relates to resinoid modifier of polyvinyl chloride (PVC) and preparation method thereof.
[background technology]
The polyvinyl chloride resin particularly poor processability of rigid polyvinyl chloride (U-PVC) resin is well-known, show that mainly plasticization temperature is approaching even be lower than decomposition temperature, melt viscosity is big, mobile poor, hot strength is poor, and intermolecular bounding force is not high, is easy to generate melt fracture, so that the products appearance variation, and use processing aid can overcome above-mentioned defective preferably.
PVC processing aid known today is that the molecule amount is 1.2 * 10
5～2.5 * 10
6Between thermoplastic elastomer, i.e. polymer polymer resin: PMMA base co-polymer (ACR resin), poly alpha methylstyrene base co-polymer (AMS resin), styrene acrylonitrile copolymer (SAN resin).
These polymers PVC processing aid generally has one or more following features:
(1) the carrying out of acceleration melting process;
(2) improve rheological property under its thermoplasticity state;
(3) improve its mechanical property under the thermo-elasticity state.
From the performance of these improvement, can obtain additional performance again.Mechanical property such as tensile strength, elongation at break, shock strength and the surface smoothness of final U-PVC goods are improved.
U.S. Rohm and Haas company just begins the research of acrylic acid or the like (PMMA class) high molecular polymer as far back as the thirties in 20th century, and develop first commodity in nineteen ninety-five, Acryloicl by name is called for short ACR, and the ACR processing aid can improve plasticizing, the processing behavior of U-PVC.
The Amoco company of the U.S. develops another kind of processing aid again to the seventies: poly alpha methylstyrene, abbreviate Resin18 (domestic title M80) as, other also has the effect of modifier as impact modifiers such as MBS, ABS, EVA, but not as the modifier effect remarkable.Up to now, active always processing aid is ACR on the market.
Polymer processing aid such as the ACR mechanism of action in the various forming methods of PVC goods is:
1, filling-rubbing effect, promptly ACR has the hard shell grain pattern, can be filled between the PVC powder and between the particle hole, and then under the mechanical ramming effect and the situation of being heated, the PVC particle is subjected to strong friction and breaks, and quickens fusion; 2, be bonded into the net effect, be that PVC is subjected to ACR duricrust friction and discharges elementary or secondary particle, particle with the rising fragmentation of frictional strength further melts, the molecule segment that the surface discharges and the synchronous fused PMMA of ACR shell molecule are bonded into complicated network after mutually, make the more approaching true melt of material to be machined, thereby improve the intensity and the extensibility of finished product.
Though ACR is the leading product in the present modifier, has some good characteristic, but also have following shortcoming as: promote plasticizing capacity still to dislike not enough in the processing, the thermostability of finished product is not enough, and the finished product surface smoothness is not high, and whiteness is poor slightly, and the synthesis technique complexity of this product, the energy consumption height, price is higher, so its application is restricted.
[summary of the invention]
At the above-mentioned defective of prior art, technical problem to be solved by this invention be to provide a kind of have more force worker's plasticizing capacity and auxiliary plasticization capacity, can promote goods coupled action and thermostability, the PVC modifier of raising product surface smooth finish;
Another technical problem to be solved by this invention be to provide that a kind of technical process is short, plant factor is high, little, the product of energy consumption need not washing, drying, the processing method of non-environmental-pollution, the above-mentioned PVC modifier of the preparation that production cost is low in the production process.
For this reason, one of technical solution of the present invention is the modifier of a kind of PVC, it is characterized in that: described modifier is or contains rare earth organic complex, and this rare earth organic complex is that polyvalent alcohol, organic acid and/or its derivative and rare earth element and/or the reaction of its oxide compound make.
Described rare earth organic complex is that light rare earths and/or its oxide compound and polyvalent alcohol, organic acid and/or its derivative carry out polycondensation and make.
Described light rare earths is meant one or more among La, Ce, Pr, Nd, the Y; Described polyvalent alcohol is one or several among ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, glycerol, tetramethylolmethane, sorbyl alcohol, the dipentaerythritol; Described organic acid and/or its derivative are selected from lauric acid, oleic acid, stearic acid, diethyl caproic acid, pentanedioic acid, hexanodioic acid, pimelic acid, certain herbaceous plants with big flowers diacid, ten dihydroxystearic acids, epoxyoleic acid, amino acid, amino Ba Dousuan, naphthylacetic acid, phenylformic acid, terephthalic acid, m-phthalic acid, maleic anhydride, Tetra hydro Phthalic anhydride, phthalic anhydride, diacetyl oxide, oxalic acid ester, maleic acid ester, phenyl ester, naphthylacetic acid ester, one or several in the amine hydroxybenzene.
Two of technical solution of the present invention is a kind of processing methodes that prepare the modifier of above-mentioned PVC, it comprises the steps: that a) control reaction temperature is between 200～300 ℃, controlling reaction time is between 0.5～2.0 hour, adopt organic acid and/or its derivative and polyvalent alcohol to carry out polycondensation and make alkyd polycondensate A, and/or adopt one or more polyvalent alcohol to carry out polycondensation to make polyethers polycondensate B; B) control reaction temperature is between 100～200 ℃, and controlling reaction time was carried out polycondensation again with the resulting polycondensate A of step a and/or B and organic acid and/or its derivative and oxidation light rare earths between 0.5～5 hour, promptly obtain described modifier.
In described step a, preferred 230～260 ℃ of temperature of reaction, preferred 1～1.5 hour of reaction times; In described step b, preferred 140～170 ℃ of temperature of reaction, preferred 2.5～4.0 hours of reaction times.
In a certain step of described polyreaction, also adding has one or several acid or the alkaline catalyzer that is selected among acetic acid, sulfuric acid, phosphorous acid, phosphoric acid, sodium hydroxide, the potassium hydroxide; The proportioning of the mol ratio of each reaction mass is as follows:
Polyvalent alcohol: 1,
Organic acid and/or its derivative: 0.1～8,
Light rare earths and/or its oxide compound: 0.01～1,
Catalyzer: 0.1～1.0% (w/w) of aforementioned base materials total amount.
Described organic alcohol is polyvalent alcohol; Described organic acid is one or several among alcohol acid, carbonylic acid, amino acid, lipid acid, alicyclic acid, the aromatic hydrocarbons acid; Described organic acid derivative be among above-mentioned organic acid acid anhydride, ester, the acid amides one or several.
The carbon skeleton of described organic acid and derivative thereof is saturated or undersaturated, and carbonatoms is C
2～C
36, have monobasic or binary carboxyl.
Described organic polyhydric alcohol is one or several among ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, glycerol, tetramethylolmethane, sorbyl alcohol, the dipentaerythritol; Described unary fatty acid is selected from one or several in lauric acid, oleic acid, stearic acid, the diethyl caproic acid; Described binary lipid acid is selected from one or several in pentanedioic acid, hexanodioic acid, pimelic acid, the certain herbaceous plants with big flowers diacid; Described alcohol acid is ten dihydroxystearic acids; Described carbonylic acid is an epoxyoleic acid; Described amino acid is amino acid and/or amino Ba Dousuan; Described alicyclic acid is naphthylacetic acid; Described aromatic hydrocarbons acid is one or several among phenylformic acid, terephthalic acid, the m-phthalic acid; Described organic acid derivative is maleic anhydride, Tetra hydro Phthalic anhydride, phthalic anhydride, diacetyl oxide, oxalic acid ester, maleic acid ester, phenyl ester, naphthylacetic acid ester, one or several in the amine hydroxybenzene.
Owing to adopted light rare earths and/or its oxide compound in the processing aid polymkeric substance, to generate the organic coordination thing, this organic coordination thing is except that all advantages with existing processing aid, can also quicken the processing plasticizing process, and has an auxiliary plastification that reduces the plasticizing moment of torsion, its coupled action that produces in goods can also improve the surface smoothness and the thermostability of finished product, improves goods initial stage whiteness.
Described technological process, owing to adopt commercially available polyvalent alcohol that is easy to get and organic acid or derivatives thereof as reaction raw materials, reaction process is simple and direct, technical process is short only two, three steps, the plant factor height, and energy consumption is little in the production process, product need not washing, drying, non-environmental-pollution, and production cost is low.
[embodiment]
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1:
In the 500ml vial of thermometer, agitator is housed, input hexanodioic acid 20g, stearic acid 80g, heating and melting stirs adding tetramethylolmethane 20g down, and glycerol 8g is warming up to 230～250 ℃ of reactions and got product A in 1 hour.
Product A is cooled to 170 ℃, add phthalic anhydride, each 20g of maleic acid ester, drop into oxidation light rare earths 4g after stirring fusion, 150～160 ℃ of insulation reaction 2 hours promptly get properties-correcting agent 1 of the present invention.
Embodiment 2:
In the 500ml vial of thermometer, agitator was housed, input glycol ether, each 110g stirring heating of sorbyl alcohol were warming up to 240～260 ℃ of insulation reaction 1.5 hours, got product B.
Product B is cooled to 140～160 ℃ drop into vinylformic acid 30g, oxidation light rare earths 10g keeps 140～160 ℃ of reactions 3～4 hours, promptly gets properties-correcting agent 2 of the present invention.
Embodiment 3:
Get product A among the embodiment one and each 110g of product B among the embodiment two, drop in the 500ml vial, about heated and stirred to 150 ℃, add methyl methacrylate 14g, maleic anhydride 30g, oxidation light rare earths 15g promptly gets properties-correcting agent 3 of the present invention in 160～170 ℃ of reactions 2.5～3.5 hours.
Below be the contrast and experiment that adopts the PVC properties-correcting agent series of the foregoing description gained to be done:
Embodiment 4:
Table one product of the present invention (WAC) and ACR401 formula test series
| The prescription number | Fixedly component: PVC:100, CPE:8, CaCO 3, lubricated-stablizer: 3.0, TiO 2：5 | |
| ??1 | Blank | |
| ??2 | ??ACR-401 | ????????????????????????1.0 |
| ??3 | ????????????????????????1.5 | |
| ??4 | ????????????????????????2.0 | |
| ??5 | ????????????????????????3.0 | |
| ??6 | Embodiment 1 product | ????????????????????????0.5 |
| ??7 | ????????????????????????0.8 | |
| ??8 | ????????????????????????1.0 | |
| ??9 | ????????????????????????1.5 | |
| ??10 | ????????????????????????2.0 | |
| ??11 | ????????????????????????3.0 | |
| ??12 | Embodiment 2 products | ????????????????????????0.8 |
| ??13 | Embodiment 3 products | ????????????????????????0.9 |
Table two PVC properties-correcting agent plasticising and plasticizing test data
From last table two as seen, add the product that modifier of the present invention is arranged in the prescription of prescription numbers 6 to 13, when its additional proportion was basic suitable with traditional ACR, the fusion time in its processing obviously descended, and the fusion time difference is at most above half a minute; Balancing torque descends obviously, the maximum 5nm. that surpasses of decline difference.In a word, the promotion of modifier of the present invention plastifies and assists plastification quite remarkable.
Embodiment 5:
Series plasticising of table three PVC properties-correcting agent and plasticizing test data:
| Sequence number | ????1 | ????2 | ????3 | ????4 | ????5 | |
| Prescription | ????PVC | ????100 | ????100 | ????100 | ????100 | ????100 |
| ????DOP | ????- | ????- | ????- | ????- | ????- | |
| ????ACR | ????- | ????2 | ????- | ????- | ????- | |
| Embodiment 1 | ????- | ????- | ????1 | ????- | ????- | |
| Embodiment 3 | ????- | ????- | ????- | ????1 | ????1 | |
| Activation lightweight CaCO 3 | ????30 | ????30 | ????30 | ????30 | ????60 | |
| Other component is identical | ||||||
| Rheological property | Fusion time | ????5′12″ | ????2′20″ | ????2′26″ | ????2′45″ | ????3′30″ |
| Balancing torque (N.M) | ????26.6 | ????27.6 | ????24.2 | ????23.9 | ????25.4 | |
| Plasticization temperature (℃) | ????191 | ????189 | ????188 | ????188 | ????193 | |
| Equilibrium temperature (℃) | ????196 | ????197 | ????195 | ????195 | ????196 | |
From last table three as seen, add the product that modifier of the present invention is arranged in the prescription of prescription sequence number 3,4,5, under the basic suitable situation with traditional ACR of additional proportion, and its fusion time and plasticization temperature and ACR's is suitable, and more blank sample all has obvious decline; Balancing torque is obvious than the decline of ACR, the maximum 3.5nm. that surpasses of decline difference.In a word, the auxiliary plastification of modifier of the present invention is quite remarkable.
Embodiment 6:
By GB/T1040-92, GB/T9341-88, GB/T1043-93 this product and ACR-401 are carried out Mechanics Performance Testing, test result sees the following form.
Table four mechanical property contrast test
| Sample | Test event | |||||
| Tensile strength (MPa) | Elongation at break (%) | Simple beam impact strength (J/m 2) | Modulus in flexure (MPa) | |||
| Processing aid | Embodiment 1 sample | ???1 # | ????42.10 | ????197.1 | ????67 | ????2647 |
| ???2 # | ????38.9 | ????104.6 | ????51 | ????1864 | ||
| ACR-401 | ???1 # | ????40.6 | ????198.1 | ????55 | ????2437 | |
| ???2 # | ????35.8 | ????105.9 | ????39.2 | ????1721 | ||
Annotate: 1
#PVC:100 CPE:8.0 processing aid: 1.5
Lubricated stablizer: 3.0 lightweight CaCO
3: 10
2
#PVC:100 CPE:8.0 processing aid: 1.5
Lubricated stablizer: 3.0 lightweight CaCO
3: 30
By last table four result as can be seen, adopt embodiment 1 product and ACR-401 contrast, simple beam impact strength improves 20% to 30%, illustrates that product of the present invention has coupled action concurrently.
Embodiment 7:
Adopt Oven Method that embodiment 2 products and ACR-401 are carried out the static heat estimation of stability, evaluation result sees the following form:
Table five static heat stability
Annotate: score value 1 (colourless) 2 (colour developing slightly) 3 (light brown reds) 4 (red-brown)
5 (dark brown reds), digestion time unit: min.
Adopt prescription: PVC (S-1000): 100 CaCO
3: 60
Stable lubricants: 4.5 processing aids: 2.0
By last table five result as can be seen, product of the present invention has effect on thermal to goods, and its sample becomes henna time ratio ACR-401 and prolongs about 30min.
Claims (9)
1, the modifier of a kind of PVC is characterized in that: described modifier is or contains rare earth organic complex, and this rare earth organic complex is that polyvalent alcohol, organic acid and/or its derivative and rare earth element and/or the reaction of its oxide compound make.
2, the modifier of a kind of PVC as claimed in claim 1 is characterized in that: described rare earth organic complex is that light rare earths and/or its oxide compound and polyvalent alcohol, organic acid and/or its derivative carry out polycondensation and make.
3, as the modifier of a kind of PVC of claim 1 or 2, it is characterized in that: described light rare earths is meant one or more among La, Ce, Pr, Nd, the Y; Described polyvalent alcohol is one or several among ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, glycerol, tetramethylolmethane, sorbyl alcohol, the dipentaerythritol; Described organic acid and/or its derivative are selected from lauric acid, oleic acid, stearic acid, diethyl caproic acid, pentanedioic acid, hexanodioic acid, pimelic acid, certain herbaceous plants with big flowers diacid, ten dihydroxystearic acids, epoxyoleic acid, amino acid, amino Ba Dousuan, naphthylacetic acid, phenylformic acid, terephthalic acid, m-phthalic acid, maleic anhydride, Tetra hydro Phthalic anhydride, phthalic anhydride, diacetyl oxide, oxalic acid ester, maleic acid ester, phenyl ester, naphthylacetic acid ester, one or several in the amine hydroxybenzene.
4, a kind of processing method for preparing the modifier of a kind of PVC as claimed in claim 1, it comprises the steps: that a) control reaction temperature is between 200～300 ℃, controlling reaction time is between 0.5～2.0 hour, adopt organic acid and/or its derivative and polyvalent alcohol to carry out polycondensation and make alkyd polycondensate A, and/or adopt one or more polyvalent alcohol to carry out polycondensation to make polyethers polycondensate B; B) control reaction temperature is between 100～200 ℃, controlling reaction time is between 0.5～5 hour, step a is made temperature of reaction between 100～200 ℃, controlling reaction time is between 0.5～5 hour, the resulting polycondensate A of step a and/or B and organic acid and/or its derivative and oxidation light rare earths are carried out polycondensation again, promptly obtain described modifier.
5, the processing method of the modifier of the described a kind of PVC of preparation as claimed in claim 4 is characterized in that: in described step a, and preferred 230～260 ℃ of temperature of reaction, preferred 1～1.5 hour of reaction times; In described step b, preferred 140～170 ℃ of temperature of reaction, preferred 2.5～4.0 hours of reaction times.
6, the processing method of the modifier of a kind of PVC of preparation as claimed in claim 5, it is characterized in that: in a certain step of described polyreaction, also adding has one or several acid or the alkaline catalyzer that is selected among acetic acid, sulfuric acid, phosphorous acid, phosphoric acid, sodium hydroxide, the potassium hydroxide; The proportioning of the mol ratio of each reaction mass is as follows:
Polyvalent alcohol: 1,
Organic acid and/or its derivative: 0.1～8,
Light rare earths and/or its oxide compound: 0.01～1,
Catalyzer: 0.1～1.0% (w/w) of aforementioned base materials total amount.
7, the processing method of the modifier of a kind of PVC of preparation as claimed in claim 6 is characterized in that: described organic alcohol is polyvalent alcohol; Described organic acid is one or several among alcohol acid, carbonylic acid, amino acid, lipid acid, alicyclic acid, the aromatic hydrocarbons acid; Described organic acid derivative be among above-mentioned organic acid acid anhydride, ester, the acid amides one or several.
8, the processing method of the modifier of a kind of PVC of preparation as claimed in claim 7 is characterized in that: the carbon skeleton of described organic acid and derivative thereof is saturated or undersaturated, and carbonatoms is C
2～C
36, have monobasic or binary carboxyl.
9, the processing method of the modifier of a kind of PVC of preparation as claimed in claim 8 is characterized in that: described organic polyhydric alcohol is one or several among ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, glycerol, tetramethylolmethane, sorbyl alcohol, the dipentaerythritol; Described unary fatty acid is selected from one or several in lauric acid, oleic acid, stearic acid, the diethyl caproic acid; Described binary lipid acid is selected from one or several in pentanedioic acid, hexanodioic acid, pimelic acid, the certain herbaceous plants with big flowers diacid; Described alcohol acid is ten dihydroxystearic acids; Described carbonylic acid is an epoxyoleic acid; Described amino acid is amino acid and/or amino Ba Dousuan; Described alicyclic acid is naphthylacetic acid; Described aromatic hydrocarbons acid is one or several among phenylformic acid, terephthalic acid, the m-phthalic acid; Described organic acid derivative is maleic anhydride, Tetra hydro Phthalic anhydride, phthalic anhydride, diacetyl oxide, oxalic acid ester, maleic acid ester, phenyl ester, naphthylacetic acid ester, one or several in the amine hydroxybenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135093 CN1212352C (en) | 2002-11-07 | 2002-11-07 | Processing modifying agent for PVC and preparing technique method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135093 CN1212352C (en) | 2002-11-07 | 2002-11-07 | Processing modifying agent for PVC and preparing technique method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1498918A true CN1498918A (en) | 2004-05-26 |
| CN1212352C CN1212352C (en) | 2005-07-27 |
Family
ID=34231452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02135093 Expired - Lifetime CN1212352C (en) | 2002-11-07 | 2002-11-07 | Processing modifying agent for PVC and preparing technique method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1212352C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717526B (en) * | 2009-10-30 | 2012-05-09 | 华南理工大学 | Method for preparing low melting point eutectic PVC heat stabilizer |
| CN102504442A (en) * | 2011-11-17 | 2012-06-20 | 山东瑞丰高分子材料股份有限公司 | External lubricant for PVC (polyvinyl chloride) |
| CN105802067A (en) * | 2016-04-07 | 2016-07-27 | 广州煌垅生物科技有限公司 | Safe and environment-friendly heat stabilizer for PVC (polyvinyl chloride) plastics and preparation method of heat stabilizer |
| CN106008938A (en) * | 2016-07-04 | 2016-10-12 | 马清洪 | PVC processing plasticizer and preparation method thereof |
-
2002
- 2002-11-07 CN CN 02135093 patent/CN1212352C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717526B (en) * | 2009-10-30 | 2012-05-09 | 华南理工大学 | Method for preparing low melting point eutectic PVC heat stabilizer |
| CN102504442A (en) * | 2011-11-17 | 2012-06-20 | 山东瑞丰高分子材料股份有限公司 | External lubricant for PVC (polyvinyl chloride) |
| CN105802067A (en) * | 2016-04-07 | 2016-07-27 | 广州煌垅生物科技有限公司 | Safe and environment-friendly heat stabilizer for PVC (polyvinyl chloride) plastics and preparation method of heat stabilizer |
| CN106008938A (en) * | 2016-07-04 | 2016-10-12 | 马清洪 | PVC processing plasticizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1212352C (en) | 2005-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102391591A (en) | Polrvinyl chloride electric power protecting sleeve and processing method thereof | |
| CN102391575B (en) | Polypropylene (PP) alloy material with low molding shrinkage and preparation method thereof | |
| CN104877118B (en) | A kind of copolyesters being adapted as 3D printed material and preparation method thereof | |
| CN1016069B (en) | The resin combination that contains smectic liquid crystal | |
| CN1035517A (en) | Polyester molding compounds | |
| CN1789332A (en) | High-performance fire-retardant polymer PC/ABS alloy | |
| CN1789333A (en) | Environmental-friendly fire-retardant PC/PBT plastic alloy | |
| CN103183935A (en) | High-ductility PBT/PC (polybutylece terephthalate/polycarbonate) alloy and preparation method thereof | |
| CN1072246C (en) | Polyethylene terephthalate resin composition | |
| CN1212352C (en) | Processing modifying agent for PVC and preparing technique method | |
| CN102504504A (en) | High-impact-resistance heat-resistant polylactic acid alloy material and preparation method thereof | |
| CN1050854C (en) | Enhancers for thermoplastic low profile additives | |
| CN111978444A (en) | Organic polyacid-based photocuring resin and preparation method and application thereof | |
| CN1887953A (en) | Modifying material for foamable polystyrene material and its prepn | |
| JP2004067997A5 (en) | ||
| CN112266589B (en) | Creep-resistant PBAT material and preparation method and application thereof | |
| CN103772952A (en) | Preparation method of multi-block thermoplastic copolyester modified polycarbonate alloy | |
| CN1152918C (en) | Powder for forming enamelled plastics and its preparing process | |
| CN1377386A (en) | Flame-retardant polyester resin composition, molded article thereof, and method of molding the same | |
| CN1214060A (en) | Polyetherester resins from diol diesters | |
| KR20120054163A (en) | Impact modifiers composition having excellent impact strength at low temperature and thermoplastic resin composition comprising the same | |
| CN106883544A (en) | A kind of polyester 3D printing material with cross-linked structure and preparation method thereof | |
| CN105801819B (en) | A kind of copolyesters for being adapted as 3D printing material and preparation method thereof | |
| CN110713700A (en) | Polyester composite material and preparation method and application thereof | |
| JP2005220214A (en) | Method for producing polyester composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: GUANGDONG WINNER NEW MATERIALS CO., LTD. Free format text: FORMER NAME: WEILINNA FUNCTIONAL MATERIAL CO., LTD., GUANGDONG |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 528521 Guangdong province city of Gao Xin Wei Tuo Liu Industrial Development Zone Patentee after: GUANGDONG WINNER NEW MATERIALS TECHNOLOGY Co.,Ltd. Address before: 528521 Guangdong province city of Gao Xin Wei Tuo Liu Industrial Development Zone Patentee before: Guangdong Winner Functional Material Co.,Ltd. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20050727 |
|
| CX01 | Expiry of patent term |