CN105331078A - Application of hyperbranched polyester to plastic processing - Google Patents
Application of hyperbranched polyester to plastic processing Download PDFInfo
- Publication number
- CN105331078A CN105331078A CN201510872311.1A CN201510872311A CN105331078A CN 105331078 A CN105331078 A CN 105331078A CN 201510872311 A CN201510872311 A CN 201510872311A CN 105331078 A CN105331078 A CN 105331078A
- Authority
- CN
- China
- Prior art keywords
- hydroxy
- polyester
- superbrnaching end
- poly
- application
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an application of hyperbranched polyester to plastic processing, and belongs to the technical field of plastic processing assistants. The application of the hyperbranched polyester to plastic processing includes the steps that by mass, 0.1% to 5% of the hydroxyl-terminated hyperbranched polyester is added into plastic; the mixture is mixed to be even, extruded, prilled and dried, and a modified plastic product is obtained. According to the application, the plastic such as PPC and the hyperbranched polyester are melted and blended, and the plastic such PPC is modified through a double-screw extruder; after the hyperbranched polyester is added into a base material of the plastic such as PPC, the effective melt viscosity of the plastic such as PPC can be remarkably reduced; in other words, processing temperature and thermal degradation are reduced; in addition, melting fluidity improved in this way can also be achieved through the small adding amount,, and extruding film forming can be more easily achieved; the tensile strength of the modified plastic such as PPC is up to 30 MPa, and the strength can be higher than the strength of thin-film-level LLDPE and the strength of thin-film-level PVC.
Description
Technical field
The invention belongs to the technical field of plastic processing additives, refer to the application of a kind of hyper-branched polyester in plastic working especially.
Background technology
Hyperbranched polymer (Hyperbranchedpolymer, HBP) is the emerging macromolecular material of a class, has 3-D solid structure, molecular structure is more regular, relative molecular mass distribution is very narrow feature.HBP has the spheroidal compact form of class, molecular entanglement is few, thus viscosity with relative molecular mass increase change less, and due in molecule with many end functional groups, the character such as viscosity, solvability, thermostability, second-order transition temperature and relative molecular mass distribution are had a significant impact.Hyperbranched polymer has the structure (tree structure) of class tree-shaped, because it is similar to branch-shape polymer, physicals also possesses the advantage similar to branch-shape polymer; But the cost of its synthesis and purifying is but low relative to branch-shape polymer.Hyperbranched polymer has good solubility, lower melt viscosity, and relative to linear polymer surface functional group very high density; Because above-mentioned feature makes HBP have good magnetism in blended applications, its special construction makes it in the physical properties improving blend, have very large potentiality, as processibility, crystallization behavior, mechanical property etc.
This product can have unique application performance in the plastics such as PP, PE, PC, PS, PPC, ABS, PET, PBT, PLA poly(lactic acid) or PA.
Hyperbranched polymer adds effective melt viscosity that significantly can reduce the plastics such as polypropylene in the plastics substrates such as polypropylene to, namely reduces processing temperature, improves the apparent property of plastics; In addition, lower addition can realize the melt fluidity strengthened so equally, can be used for complicated or thin articles injection-moulded; Improve the yield strength of plastics, tensile modulus, Notched Izod Impact Strength and flexural strength, and then improve mechanical property and the processing characteristics of plastics; Overcome melt viscosity in plastic processes larger, mobility is poor, it is shaping that lesser temps is difficult to processing plasticizing, the not full and macroscopic irregularity such as current mark, crazing of large-scale injection molding, the injection moulding of thin-walled injection molding part, can also overcome the performance deficiency that blown film outward appearance is rough, film bubble is unstable, became uneven is even.
Such as: in the melt-processed process of PPC, thermal destruction occurs in more than 219 DEG C of temperature, and this will have a strong impact on the performance of product.Degradable plastics PPC the most, is applied to plastics film field, and tensile strength does not far reach film-grade LLDPE and PVC; More few better in line with interpolation auxiliary agent content, ensure the degradation amount of PPC, the auxiliary agent that existing interpolation content is lower cannot realize the effect improving intensity as far as possible.
Summary of the invention
The invention provides the application of a kind of hyper-branched polyester in plastic working, solve that plastic hot degradation temperature in prior art is high and tensile strength is not enough and limit its problem applied.
The application of a kind of hyper-branched polyester of the present invention in plastic working, it mainly realizes by the following technical programs so in addition: join in plastics by superbrnaching end-hydroxy polyester according to the addition that mass percent is 0.1-5%, mix, extruding pelletization, drying, obtains the plastic prod of modification.
As the preferred embodiment of one, comprise the following steps: 1) superbrnaching end-hydroxy polyester is dry, for subsequent use; 2) get the superbrnaching end-hydroxy polyester of plastics and step 1) gained, mixing, obtains mixture, for subsequent use; 3) twin screw extruder is warmed up to 160-170 DEG C, after preheating 1-2h, by step 2) gained mixture, drops into twin screw extruder, extruding pelletization; 4) particle step 3) produced, at 50 DEG C, dry 1-2h, obtains the plastic prod of modification.
As the preferred embodiment of one, the preparation method of described superbrnaching end-hydroxy polyester is: in polyol compound, add poly-hydroxy carboxylic compound, and add catalyzer, poly-hydroxy carboxylic compound is 3-16:1 with the ratio of the molar mass of polyol compound, and the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass; Under protection of inert gas, be warming up to 120-180 DEG C, reaction 2-8h; Then, at reduced pressure conditions, reaction is proceeded; When the acid number of reaction is less than 30mgKOH/g, reaction terminates, and obtains first-generation superbrnaching end-hydroxy polyester, and end functional group number is 6-32; In first-generation superbrnaching end-hydroxy polyester, continue to add poly-hydroxy carboxylic compound and catalyzer, the addition of poly-hydroxy carboxylic compound is 6-32 times of polyol compound molar mass, the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain s-generation superbrnaching end-hydroxy polyester, end functional group number is 12-64; In s-generation superbrnaching end-hydroxy polyester, continue to add poly-hydroxy carboxylic compound and catalyzer, the addition of poly-hydroxy carboxylic compound is 12-64 times of polyol compound molar mass, the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain third generation superbrnaching end-hydroxy polyester, end functional group number is 24-128; By that analogy, obtain N-Generation superbrnaching end-hydroxy polyester, N is natural number, and functional group number is 3 × 2
n-16 × 2
nindividual.
As the preferred embodiment of one, the temperature of described reaction is 160 DEG C, and described reduced pressure is Absolute truth reciprocal of duty cycle is-0.1MPa to-0.07MPa.
As the preferred embodiment of one, described superbrnaching end-hydroxy polyester is one or more in first-generation superbrnaching end-hydroxy polyester, s-generation superbrnaching end-hydroxy polyester, third generation superbrnaching end-hydroxy polyester, forth generation superbrnaching end-hydroxy polyester, the 5th generation superbrnaching end-hydroxy polyester.
As the preferred embodiment of one, described polyol compound is the derivative of polyvalent alcohol or polyvalent alcohol, and described polyvalent alcohol is one or more in tetramethylolmethane, TriMethylolPropane(TMP), glycerol, dipentaerythritol; Described poly-hydroxy carboxylic compound is one or more in polycarboxylic acid, multi-hydroxy carboxy acid, poly-hydroxy acid anhydrides; Described catalyzer is one or more in tosic acid, butyl (tetra) titanate, dibutyl tin laurate, stannous octoate.
As the preferred embodiment of one, the addition of described superbrnaching end-hydroxy polyester is 0.5-1%, and its decomposition temperature is 268 DEG C.
As the preferred embodiment of one, in described step 3), there is 5-12 temperature control district in twin screw extruder, and the processing temperature in each temperature control district is 160 DEG C.
As the preferred embodiment of one, in described step 1), superbrnaching end-hydroxy polyester carries out drying under room temperature in vacuum drying oven, and time of drying is 5-7h; In described step 4), particle carries out drying in convection oven.
As the preferred embodiment of one, described step 2) in, plastics and superbrnaching end-hydroxy polyester mix in high-speed mixer, and mixing time is 3-6min, and mixing velocity is 700-1500r/min; Described plastics are one or more in PPC, ABS, PET, PBT, PLA poly(lactic acid), PP, PE, PC, PS or PA.The preferred PPC of the present invention has carried out systematic difference research as application system.
Beneficial effect of the present invention: the plastics such as PPC of the present invention and hyper-branched polyester melt blended material also carry out modification by twin screw extruder to plastics such as PPC, hyper-branched polyester adds effective melt viscosity that significantly can reduce the plastics such as PPC in the plastics substrates such as PPC to, namely reduces processing temperature and thermal destruction; In addition, lower addition can realize the melt fluidity strengthened so equally, can film extrusion more easily; The tensile strength of the plastics such as modified PPC reaches 30MPa, and intensity can exceed film-grade LLDPE and PVC.This hyper-branched polyester can be used as the processing aid of the plastics such as PPC, reduces processing temperature and current of electric, improves the apparent mass of the plastics such as PPC; Hyper-branched polyester decomposition temperature is higher, reaches 268 DEG C; Hyper-branched polyester effectively improves the mechanical property of the plastics films such as PPC, and it is lower to add content; Hyper-branched polyester may be used for suitability for industrialized production, cost is low, industrialization promotion is easy; Reduce the plastic working costs such as PPC, addition is few compared with similar products, and cost is low.
Embodiment
Be clearly and completely described technical scheme of the present invention below in conjunction with specific embodiments of the invention, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
embodiment one
Superbrnaching end-hydroxy polyester is joined in PPC according to the addition that mass percent is 0.1%, mixes, extruding pelletization, dry, obtain the PPC product of modification.
In the present invention, the addition of superbrnaching end-hydroxy polyester adopts mass percent to represent, namely addition adopts the ratio of the quality of superbrnaching end-hydroxy polyester and the quality of PPC to represent; Such as in the present embodiment, the addition of superbrnaching end-hydroxy polyester is 0.1%, namely in quality is to add the superbrnaching end-hydroxy polyester that quality is 0.1 part in the PPC of 100 parts.
embodiment two
Superbrnaching end-hydroxy polyester is joined in PPC with the addition that mass percentage is 5%, mixes, extruding pelletization, dry, obtain the PPC product of modification.
embodiment three
Superbrnaching end-hydroxy polyester is dry, for subsequent use; Get PPC and above-mentioned superbrnaching end-hydroxy polyester, mixing, obtain mixture, now the addition of superbrnaching end-hydroxy polyester is 1%, for subsequent use; Twin screw extruder is warmed up to 160 DEG C, after preheating 1h, by said mixture, drops into twin screw extruder, extruding pelletization; By the particle produced, at 50 DEG C, dry 1h, obtains the PPC product of modification.
embodiment four
Superbrnaching end-hydroxy polyester is dry, for subsequent use; Get PPC and above-mentioned superbrnaching end-hydroxy polyester, mixing, obtain mixture, now the addition of superbrnaching end-hydroxy polyester is 0.5%, for subsequent use; Twin screw extruder is warmed up to 170 DEG C, after preheating 2h, by said mixture, drops into twin screw extruder, extruding pelletization; By the particle produced, at 50 DEG C, dry 2h, obtains the PPC product of modification.
embodiment five
By superbrnaching end-hydroxy polyester under room temperature at the dry 5h of vacuum drying oven, be put in dry seal cavity and preserve, this material be white or light yellow solid or thick liquid; PPC and hyper-branched polyester are put in the high-speed mixer of 1500r/min and mix 3min, and wherein, the addition of superbrnaching end-hydroxy polyester is 0.25%; Then, import in hermetically drying hopper, for subsequent use; Twin screw extruder 10 warm areas are heated to 160 DEG C, after preheating 1h, blanking extruding pelletization; Then, the particle produced is put in dry 1h in 50 DEG C of convection oven temperature, obtains the PPC product of modification.
embodiment six
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add dimethylol propionic acid 482Kg and tetramethylolmethane 122Kg, add 3Kg stannous octoate catalyst, under nitrogen protection, be heated to 160 DEG C, reaction 6h; Under vacuumized conditions, continue reaction, when the acid number of reaction is less than 30mgKOH/g, reaction terminates, and cooling, obtain water white transparency solid, be first-generation superbrnaching end-hydroxy polyester, be denoted as HBPE-10, terminal hydroxy group number is 8.
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 225KgHBPE-10 and 402Kg dimethylol propionic acid, add 3.135Kg tosic acid, under nitrogen protection, be heated to 160 DEG C, reaction 4h; Under vacuumized conditions, continue reaction, when the acid number of reaction is less than 30mgKOH/g, reaction terminates, and cooling, obtain water white transparency solid, be s-generation superbrnaching end-hydroxy polyester, be denoted as HBPE-20, its end functional group number is 16.
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 260KgHBPE-20 and 364Kg dimethylol propionic acid, add 3.12Kg tosic acid, under nitrogen protection, be heated to 160 DEG C, reaction 4h; Under vacuumized conditions, continue reaction, when the acid number of reaction is less than 30mgKOH/g, reaction terminates, and cooling, obtain water white transparency solid, be third generation superbrnaching end-hydroxy polyester, be denoted as HBPE-30, terminal hydroxy group number is 32.
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 290KgHBPE-30 and 367Kg dimethylol propionic acid, add 3.28Kg tosic acid, under nitrogen gas protection, be heated to 160 DEG C, reaction 3h; Under vacuumized conditions, continue reaction, when the acid number of reaction is less than 30mgKOH/g, reaction terminates, and cooling, obtain water white transparency solid, be forth generation superbrnaching end-hydroxy polyester, be denoted as HBPE-40, terminal hydroxy group number is 64.
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 290KgHBPE-40 and 350Kg dimethylol propionic acid, add 3.2Kg tosic acid, under nitrogen gas protection, be heated to 140 DEG C, reaction 3h; Under vacuumized conditions, continue reaction, when reaction acid number be less than 30mgKOH/g, reaction terminate, cooling, obtain water white transparency solid, be the 5th generation superbrnaching end-hydroxy polyester, be denoted as HBPE-50, terminal hydroxy group number is 128.
By above-mentioned s-generation superbrnaching end-hydroxy polyester (HBPE-20) under room temperature at the dry 7h of vacuum drying oven, be put in dry seal cavity and preserve, this material be white or light yellow solid; PPC and hyper-branched polyester are put in high-speed mixer and mix 6min, and wherein, the addition of superbrnaching end-hydroxy polyester is 0.45%; Then, import in hermetically drying hopper, for subsequent use; Twin screw extruder 5 warm areas are all heated to 160 DEG C, after preheating 1.5h, blanking extruding pelletization; Then, the particle produced is put in dry 1.5h in 50 DEG C of convection oven temperature, obtains the PPC product of modification.
embodiment seven
Forth generation superbrnaching end-hydroxy polyester (HBPE-40) prepared by Example six, at the dry 6h of vacuum drying oven under room temperature, is put in dry seal cavity and preserves; Get PPC and above-mentioned superbrnaching end-hydroxy polyester to be put in the high-speed mixer of 700r/min and to mix 4min, wherein, the addition of superbrnaching end-hydroxy polyester is 0.65%; Then, import in hermetically drying hopper, for subsequent use; Twin screw extruder 12 warm areas are all heated to 160 DEG C, after preheating 1h, blanking extruding pelletization; Then, the particle produced is put in the convection oven temperature of 50 DEG C, dry 1h, obtains the PPC product of modification.
Certainly, in the present invention, superbrnaching end-hydroxy polyester also can be in HBPE-10, HBPE-20, HBPE-30, HBPE-40, HBPE-50 other any one or multiple mixture; Here PPC plastics can also be one or more in ABS, PET, PBT, PLA poly(lactic acid), PP, PE, PC, PS or PA.
By seven of the embodiment of the present invention one to embodiment seven kinds of MODIFIED PP C and standard batten, carry out Mechanics Performance Testing experiment respectively, its tensile strength and elongation at break is measured according to the method for GB/T1040-2006, its thermal distorsion temperature (HDT) is measured according to the method for GB/T1633-2000, its melting index (abbreviation melting means) is measured according to the method for GB/T3682-2000, and carrying out thermogravimetric analysis (TGA) with the speed of 10 DEG C/min, experimental results is as shown in table 1.
As can be seen from Table 1, through the PPC that superbrnaching end-hydroxy polyester is modified, its tensile strength obviously strengthens, and its ultimate tensile strength can reach 30MPa, greatly improves its mechanical property; Meanwhile, its elongation at break significance declines, and drops to 3.32-5.98%, has good cutting performance; Its HDT remains unchanged substantially, and namely modified PPC is the same with pure PPC maintains good processing heat stability; In thermogravimetric analysis experiment, the temperature of modified PPC when thermogravimetric weight loss 95% and pure PPC basically identical, illustrate the thermal degradation temperature of modified PPC and pure PPC basically identical; The purer PPC of its melting index obviously declines, and modified PPC suitably reduces the flowing property adding man-hour; And in the process of PPC modification, the addition of superbrnaching end-hydroxy polyester is few, easy to process.
The physicals of table 1PPC/ superbrnaching end-hydroxy polyester
Beneficial effect of the present invention: the plastics such as PPC of the present invention and hyper-branched polyester melt blended material also carry out modification by twin screw extruder to plastics such as PPC, hyper-branched polyester adds effective melt viscosity that significantly can reduce the plastics such as PPC in the plastics substrates such as PPC to, namely reduces processing temperature and thermal destruction; In addition, lower addition can realize the melt fluidity strengthened so equally, can film extrusion more easily; The tensile strength of the plastics such as modified PPC can reach 30MPa, and intensity can exceed film-grade LLDPE and PVC.Hyper-branched polyester can be used as the processing aid of the plastics such as PPC, reduces processing temperature and current of electric, improves the apparent mass of the plastics such as PPC; Hyper-branched polyester decomposition temperature is higher, reaches 268 DEG C; Hyper-branched polyester effectively improves the mechanical property of the plastics films such as PPC, and its addition is lower; Hyper-branched polyester is used for suitability for industrialized production, cost is low, industrialization promotion is easy; Reduce the tooling cost of the plastics such as PPC, addition is few compared with similar products, and cost is low.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the application of hyper-branched polyester in plastic working, is characterized in that:
Superbrnaching end-hydroxy polyester is joined in plastics according to the addition that mass percent is 0.1-5%, mixes, extruding pelletization, dry, obtain the plastic prod of modification.
2. the application of hyper-branched polyester according to claim 1 in plastic working, is characterized in that: comprise the following steps:
1) superbrnaching end-hydroxy polyester is dry, for subsequent use;
2) get the superbrnaching end-hydroxy polyester of plastics and step 1) gained, mixing, obtains mixture, for subsequent use;
3) twin screw extruder is warmed up to 160-170 DEG C, after preheating 1-2h, by step 2) gained mixture, drops into twin screw extruder, extruding pelletization;
4) particle step 3) produced, at 50 DEG C, dry 1-2h, obtains the plastic prod of modification.
3. the application of hyper-branched polyester according to claim 1 and 2 in plastic working, is characterized in that, the preparation method of described superbrnaching end-hydroxy polyester is:
In polyol compound, add poly-hydroxy carboxylic compound, and adding catalyzer, poly-hydroxy carboxylic compound is 3-16:1 with the ratio of the molar mass of polyol compound, and the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass;
Under protection of inert gas, be warming up to 120-180 DEG C, reaction 2-8h; Then, at reduced pressure conditions, reaction is proceeded; When the acid number of reaction is less than 30mgKOH/g, reaction terminates, and obtains first-generation superbrnaching end-hydroxy polyester, and end functional group number is 6-32;
In first-generation superbrnaching end-hydroxy polyester, continue to add poly-hydroxy carboxylic compound and catalyzer, the addition of poly-hydroxy carboxylic compound is 6-32 times of polyol compound molar mass, the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain s-generation superbrnaching end-hydroxy polyester, end functional group number is 12-64;
In s-generation superbrnaching end-hydroxy polyester, continue to add poly-hydroxy carboxylic compound and catalyzer, the addition of poly-hydroxy carboxylic compound is 12-64 times of polyol compound molar mass, the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain third generation superbrnaching end-hydroxy polyester, end functional group number is 24-128;
By that analogy, obtain N-Generation superbrnaching end-hydroxy polyester, N is natural number, and functional group number is 3 × 2
n-16 × 2
nindividual.
4. the application of hyper-branched polyester according to claim 3 in plastic working, is characterized in that:
The temperature of described reaction is 160 DEG C, and described reduced pressure is Absolute truth reciprocal of duty cycle is-0.1MPa to-0.07MPa.
5. the application of hyper-branched polyester according to claim 4 in plastic working, is characterized in that:
Described superbrnaching end-hydroxy polyester is one or more in first-generation superbrnaching end-hydroxy polyester, s-generation superbrnaching end-hydroxy polyester, third generation superbrnaching end-hydroxy polyester, forth generation superbrnaching end-hydroxy polyester, the 5th generation superbrnaching end-hydroxy polyester.
6. the application of hyper-branched polyester according to claim 3 in plastic working, is characterized in that:
Described polyol compound is the derivative of polyvalent alcohol or polyvalent alcohol, and described polyvalent alcohol is one or more in tetramethylolmethane, TriMethylolPropane(TMP), glycerol, dipentaerythritol;
Described poly-hydroxy carboxylic compound is one or more in polycarboxylic acid, multi-hydroxy carboxy acid, poly-hydroxy acid anhydrides;
Described catalyzer is one or more in tosic acid, butyl (tetra) titanate, dibutyl tin laurate, stannous octoate.
7. the application of hyper-branched polyester according to claim 1 and 2 in plastic working, is characterized in that:
The addition of described superbrnaching end-hydroxy polyester is 0.5-1%, and its decomposition temperature is 268 DEG C.
8. the application of hyper-branched polyester according to claim 2 in plastic working, is characterized in that:
In described step 3), there is 5-12 temperature control district in twin screw extruder, and the processing temperature in each temperature control district is 160 DEG C.
9. the application of hyper-branched polyester according to claim 8 in plastic working, is characterized in that:
In described step 1), superbrnaching end-hydroxy polyester carries out drying under room temperature in vacuum drying oven, and time of drying is 5-7h;
In described step 4), particle carries out drying in convection oven.
10. the application of hyper-branched polyester according to claim 9 in plastic working, is characterized in that:
Described step 2) in, plastics and superbrnaching end-hydroxy polyester mix in high-speed mixer, and mixing time is 3-6min, and mixing velocity is 700-1500r/min;
Described plastics are one or more in PPC, ABS, PET, PBT, PLA poly(lactic acid), PP, PE, PC, PS or PA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510872311.1A CN105331078A (en) | 2015-12-02 | 2015-12-02 | Application of hyperbranched polyester to plastic processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510872311.1A CN105331078A (en) | 2015-12-02 | 2015-12-02 | Application of hyperbranched polyester to plastic processing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105331078A true CN105331078A (en) | 2016-02-17 |
Family
ID=55281856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510872311.1A Pending CN105331078A (en) | 2015-12-02 | 2015-12-02 | Application of hyperbranched polyester to plastic processing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105331078A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754260A (en) * | 2016-05-11 | 2016-07-13 | 江南大学 | Low-migrated-amount PVC bottle cap sealant and preparation method thereof |
| CN107540975A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of high rush-resistant polyvinyl chloride water-feeding pipes and preparation method thereof |
| CN108250565A (en) * | 2017-12-19 | 2018-07-06 | 广东聚石化学股份有限公司 | A kind of high fluidity for coil rack halogen-free expanded flame-retardant glass fiber reinforced polypropylene composite material resistant to bending and preparation method thereof |
| CN108250566A (en) * | 2017-12-19 | 2018-07-06 | 广东聚石化学股份有限公司 | A kind of low warpage halogen-free expanded flame-retardant Long Glass Fiber Reinforced PP Composite and preparation method thereof |
| CN108530853A (en) * | 2018-05-17 | 2018-09-14 | 北京工商大学 | A kind of derivative blended objects of PLA/HBP and preparation method thereof |
| CN108707323A (en) * | 2018-05-17 | 2018-10-26 | 北京工商大学 | A kind of derivative blended objects of PLA/PPC/HBP and preparation method thereof |
| CN109666277A (en) * | 2018-11-21 | 2019-04-23 | 苏州市同发塑业有限公司 | A kind of fiber reinforcement delustring fire retardation PC/ABS alloy and preparation method thereof |
| CN109749372A (en) * | 2018-12-30 | 2019-05-14 | 聚石化学(苏州)有限公司 | A kind of fire-retardant reinforced PBT composite material and preparation method thereof |
| CN109867922A (en) * | 2018-12-28 | 2019-06-11 | 聚石化学(苏州)有限公司 | A kind of and excellent halogen free flame-retardant reinforced PBT composite material and preparation method thereof of adhering with epoxy resin |
| WO2019121356A1 (en) | 2017-12-21 | 2019-06-27 | Covestro Deutschland Ag | Polycarbonate composition |
| CN110551381A (en) * | 2018-06-01 | 2019-12-10 | 汉达精密电子(昆山)有限公司 | High-flow flame-retardant PC/ABS carbon nanotube conductive material and product thereof |
| CN110922676A (en) * | 2019-10-30 | 2020-03-27 | 中化石化销售有限公司 | Preparation method of foaming agent master batch |
| CN110964332A (en) * | 2019-12-02 | 2020-04-07 | 北京林业大学 | Hyperbranched polyester toughened and reinforced high-strength recyclable soybean protein film and preparation method thereof |
| CN111072933A (en) * | 2018-10-19 | 2020-04-28 | 长春工业大学 | Preparation of double-layer radial polycaprolactone |
| CN111303388A (en) * | 2020-03-16 | 2020-06-19 | 东华大学 | Preparation method of hydrolysis-resistant PBT polyester resin |
| CN111363125A (en) * | 2020-04-08 | 2020-07-03 | 武汉超支化树脂科技有限公司 | Carboxyl-terminated hyperbranched polyester for processing polylactic acid and preparation method and application thereof |
| CN111893587A (en) * | 2020-08-12 | 2020-11-06 | 中润科技股份有限公司 | Processing method of PBT (polybutylene terephthalate) polyester fiber for woolen sweater |
| CN112266589A (en) * | 2020-11-06 | 2021-01-26 | 合聚高分子材料科技(广东)有限公司 | Creep-resistant PBAT material and preparation method and application thereof |
| CN112745487A (en) * | 2020-12-29 | 2021-05-04 | 威海晨源分子新材料有限公司 | Fan-shaped hyperbranched polyester/amide ester, and preparation method and application thereof |
| CN113402868A (en) * | 2021-07-12 | 2021-09-17 | 北京化工大学常州先进材料研究院 | Preparation method of hyperbranched polyester modified polylactic acid/polypropylene carbonate composite material |
| CN113698726A (en) * | 2021-09-14 | 2021-11-26 | 青岛中新华美塑料有限公司 | High-filling high-performance flame-retardant ABS material and preparation method thereof |
| CN114075342A (en) * | 2020-08-11 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of PET (polyethylene terephthalate) film and PET-based printing paper film |
| CN115340666A (en) * | 2022-08-10 | 2022-11-15 | 华润化学材料科技股份有限公司 | Hydroxyl-terminated hyperbranched polymer and preparation method and application thereof |
| CN116143998A (en) * | 2023-03-13 | 2023-05-23 | 上海交通大学 | Bio-based hydroxyl-terminated hyperbranched polyester, preparation method thereof and application thereof as plasticizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242627A (en) * | 2013-03-27 | 2013-08-14 | 宋雪晶 | Application of fatty acid ester end group hyperbranched polyester as high polymer material viscosity reducing and toughening agent |
| CN104559152A (en) * | 2014-12-19 | 2015-04-29 | 威海晨源分子新材料有限公司 | Application of hyperbranched polyester in PA6 (polyamide 6) |
-
2015
- 2015-12-02 CN CN201510872311.1A patent/CN105331078A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242627A (en) * | 2013-03-27 | 2013-08-14 | 宋雪晶 | Application of fatty acid ester end group hyperbranched polyester as high polymer material viscosity reducing and toughening agent |
| CN104559152A (en) * | 2014-12-19 | 2015-04-29 | 威海晨源分子新材料有限公司 | Application of hyperbranched polyester in PA6 (polyamide 6) |
Non-Patent Citations (1)
| Title |
|---|
| 高治等: "Boltorn型超支化聚酯的合成及应用", 《石化技术与应用》 * |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754260A (en) * | 2016-05-11 | 2016-07-13 | 江南大学 | Low-migrated-amount PVC bottle cap sealant and preparation method thereof |
| CN107540975A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of high rush-resistant polyvinyl chloride water-feeding pipes and preparation method thereof |
| CN107540975B (en) * | 2016-06-29 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of high rush-resistant polyvinyl chloride water-feeding pipes and preparation method thereof |
| CN108250565A (en) * | 2017-12-19 | 2018-07-06 | 广东聚石化学股份有限公司 | A kind of high fluidity for coil rack halogen-free expanded flame-retardant glass fiber reinforced polypropylene composite material resistant to bending and preparation method thereof |
| CN108250566A (en) * | 2017-12-19 | 2018-07-06 | 广东聚石化学股份有限公司 | A kind of low warpage halogen-free expanded flame-retardant Long Glass Fiber Reinforced PP Composite and preparation method thereof |
| CN108250565B (en) * | 2017-12-19 | 2020-08-18 | 广东聚石化学股份有限公司 | High-fluidity bending-resistant halogen-free expansion flame-retardant glass fiber reinforced polypropylene composite material for coil framework and preparation method thereof |
| CN108250566B (en) * | 2017-12-19 | 2020-08-18 | 广东聚石化学股份有限公司 | Low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof |
| WO2019121356A1 (en) | 2017-12-21 | 2019-06-27 | Covestro Deutschland Ag | Polycarbonate composition |
| CN108707323A (en) * | 2018-05-17 | 2018-10-26 | 北京工商大学 | A kind of derivative blended objects of PLA/PPC/HBP and preparation method thereof |
| CN108530853A (en) * | 2018-05-17 | 2018-09-14 | 北京工商大学 | A kind of derivative blended objects of PLA/HBP and preparation method thereof |
| CN110551381A (en) * | 2018-06-01 | 2019-12-10 | 汉达精密电子(昆山)有限公司 | High-flow flame-retardant PC/ABS carbon nanotube conductive material and product thereof |
| CN111072933A (en) * | 2018-10-19 | 2020-04-28 | 长春工业大学 | Preparation of double-layer radial polycaprolactone |
| CN109666277A (en) * | 2018-11-21 | 2019-04-23 | 苏州市同发塑业有限公司 | A kind of fiber reinforcement delustring fire retardation PC/ABS alloy and preparation method thereof |
| CN109666277B (en) * | 2018-11-21 | 2021-12-31 | 苏州市同发塑业有限公司 | Fiber-reinforced extinction flame-retardant PC/ABS alloy and preparation method thereof |
| CN109867922A (en) * | 2018-12-28 | 2019-06-11 | 聚石化学(苏州)有限公司 | A kind of and excellent halogen free flame-retardant reinforced PBT composite material and preparation method thereof of adhering with epoxy resin |
| CN109749372A (en) * | 2018-12-30 | 2019-05-14 | 聚石化学(苏州)有限公司 | A kind of fire-retardant reinforced PBT composite material and preparation method thereof |
| CN110922676A (en) * | 2019-10-30 | 2020-03-27 | 中化石化销售有限公司 | Preparation method of foaming agent master batch |
| CN110922676B (en) * | 2019-10-30 | 2022-09-16 | 中化石化销售有限公司 | Preparation method of foaming agent master batch |
| CN110964332A (en) * | 2019-12-02 | 2020-04-07 | 北京林业大学 | Hyperbranched polyester toughened and reinforced high-strength recyclable soybean protein film and preparation method thereof |
| CN110964332B (en) * | 2019-12-02 | 2021-07-27 | 北京林业大学 | Hyperbranched polyester toughened and reinforced high-strength recyclable soybean protein film and preparation method thereof |
| CN111303388A (en) * | 2020-03-16 | 2020-06-19 | 东华大学 | Preparation method of hydrolysis-resistant PBT polyester resin |
| CN111363125A (en) * | 2020-04-08 | 2020-07-03 | 武汉超支化树脂科技有限公司 | Carboxyl-terminated hyperbranched polyester for processing polylactic acid and preparation method and application thereof |
| CN114075342A (en) * | 2020-08-11 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of PET (polyethylene terephthalate) film and PET-based printing paper film |
| CN114075342B (en) * | 2020-08-11 | 2023-11-17 | 中国石油化工股份有限公司 | Preparation method of PET film and PET-based printing paper coating film |
| CN111893587A (en) * | 2020-08-12 | 2020-11-06 | 中润科技股份有限公司 | Processing method of PBT (polybutylene terephthalate) polyester fiber for woolen sweater |
| CN112266589A (en) * | 2020-11-06 | 2021-01-26 | 合聚高分子材料科技(广东)有限公司 | Creep-resistant PBAT material and preparation method and application thereof |
| CN112745487A (en) * | 2020-12-29 | 2021-05-04 | 威海晨源分子新材料有限公司 | Fan-shaped hyperbranched polyester/amide ester, and preparation method and application thereof |
| CN113402868A (en) * | 2021-07-12 | 2021-09-17 | 北京化工大学常州先进材料研究院 | Preparation method of hyperbranched polyester modified polylactic acid/polypropylene carbonate composite material |
| CN113698726A (en) * | 2021-09-14 | 2021-11-26 | 青岛中新华美塑料有限公司 | High-filling high-performance flame-retardant ABS material and preparation method thereof |
| CN115340666A (en) * | 2022-08-10 | 2022-11-15 | 华润化学材料科技股份有限公司 | Hydroxyl-terminated hyperbranched polymer and preparation method and application thereof |
| CN116143998A (en) * | 2023-03-13 | 2023-05-23 | 上海交通大学 | Bio-based hydroxyl-terminated hyperbranched polyester, preparation method thereof and application thereof as plasticizer |
| CN116143998B (en) * | 2023-03-13 | 2024-09-17 | 上海交通大学 | Bio-based hydroxyl-terminated hyperbranched polyester, preparation method thereof and application thereof as plasticizer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105331078A (en) | Application of hyperbranched polyester to plastic processing | |
| CN105315441A (en) | Application of fatty acid modified hyperbranched polyester to plastic processing | |
| TWI705094B (en) | Recycle pet foaming material and method for manufacturing the same | |
| CN102108196B (en) | Method for preparing polylactic acid degradable material | |
| CN105385137A (en) | Application of hyperbranched poly(amide amine)s in plastic processing | |
| CN105585831A (en) | Polycarbonate/polybutylene terephthalate alloy material as well as preparation method and application thereof | |
| CN104387732A (en) | Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof | |
| CN110128804A (en) | A method of improving polyhydroxyalkanoate melt-processable and mechanical property | |
| CN104629280A (en) | High-strength high-toughness polyactic acid composite material suitable for 3D printing molding and preparation method of composite material | |
| CN114230989A (en) | Preparation method of environment-friendly biodegradable PBAT (poly (butylene adipate-co-terephthalate)) foaming material | |
| CN103396659A (en) | Method for accelerating crystallization of polylactic acid resin | |
| CN100497458C (en) | Biologically degradable starch base high molecular composition, film made thereof, and its preparing method | |
| CN102206406B (en) | Method for preparing transparent heat-resistance polylactic acid modification material | |
| CN109721786B (en) | Polyethylene composite material and preparation method thereof | |
| CN114773810A (en) | High-performance polylactic acid-based 3D printing wire rod and preparation method thereof | |
| CN111531741B (en) | Device and method for preparing modified polylactic acid material on line by polylactic acid melt | |
| CN103059530B (en) | Composite material for producing disposable plastic products and preparation method of composite material | |
| CN102875987B (en) | A kind of organic nucleating agent and its preparation and application | |
| CN101225222A (en) | Polylactic acid as well as derivative composite material and preparation method thereof | |
| CN108384200B (en) | Quickly crystallized PBAT material and preparation method thereof | |
| CN116891623A (en) | Biological full-degradable material and preparation method thereof | |
| CN103965600A (en) | Method for toughening heat-resistant modified polylactic acid with plant-base composite environment-friendly modifier | |
| CN108384173A (en) | A kind of high molecular weight height founds the preparation method of structure lactic acid composite material | |
| CN111286164B (en) | Biodegradable plastic and preparation method thereof | |
| CN110294910B (en) | High-temperature water-soluble polyvinyl alcohol master batch and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160217 |
|
| RJ01 | Rejection of invention patent application after publication |