CN105385137A - Application of hyperbranched poly(amide amine)s in plastic processing - Google Patents
Application of hyperbranched poly(amide amine)s in plastic processing Download PDFInfo
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- CN105385137A CN105385137A CN201510872312.6A CN201510872312A CN105385137A CN 105385137 A CN105385137 A CN 105385137A CN 201510872312 A CN201510872312 A CN 201510872312A CN 105385137 A CN105385137 A CN 105385137A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92209—Temperature
Abstract
The invention discloses application of hyperbranched poly(amide amine)s in plastic processing, and belongs to the technical field of plastic processing agents. The application provided by the invention comprises the steps of uniformly mixing 0.1 to 5 parts by weight of amino-terminated hyperbranched poly(amide amine)s and 100 parts by weight of plastic, performing extrusion pelletization, and drying to obtain a modified plastic product. According to the application provided by the invention, the hyperbranched poly(amide amine)s is taken as a processing agent of the plastic of PPC, PP, PE, PA and the like, the outer layer of a hyperbranched poly(amide amine)s molecule contains a large number of active functional groups, and is low in melt viscosity, by adding the hyperbranched poly(amide amine)s into plastic substrates of PPC, PP, PE, PA and the like, the effective melt viscosity of a plastic system can be significantly reduced, namely the processing temperature and thermal degradation are decreased; in addition, such enhanced melt fluidity can still be realized through a lower additive amount, a finished film can be more easily extruded out, and the tensile strength and the processing performance of the plastic of PPC, PP, PE, PA and the like are greatly increased.
Description
Technical field
The invention belongs to the technical field of plastic processing additives, refer to the application of a kind of over-branched polyamidoamine 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 over-branched polyamidoamine in plastic working, solve plastic working poor heat stability in prior art and limit its problem applied.
The application of a kind of over-branched polyamidoamine of the present invention in plastic working, it mainly realizes by the following technical programs so in addition: the amine-terminated hyperbrancedization daiamid of 0.1-5 weight part and the plastics of 100 weight parts are mixed, extruding pelletization, dry, obtain the plastic prod of modification.
As the preferred embodiment of one, comprise the following steps: 1) amine-terminated hyperbrancedization daiamid is dry, for subsequent use; 2) get the amine-terminated hyperbrancedization daiamid 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 amine-terminated hyperbrancedization daiamid is: a) under ice bath, is added drop-wise in the methanol solution of amine monomers, obtains mixing solutions by the methanol solution of esters monomer; B) by step a) gained mixing solutions, under protection of inert gas, at room temperature, reaction 30-55h, and underpressure distillation is carried out at 55-65 DEG C, obtain thick product; C) by thick for step b) gained product, at 110-160 DEG C, reaction 2-7h, obtains amine-terminated hyperbrancedization daiamid product.
As the preferred embodiment of one, the mol ratio of described amine monomers and described esters monomer is 1:1.5-3.5, and amine monomers and esters monomer total mass account for the 10-30% of mixing solutions total mass; Described amine monomers is polyamino amine, and described polyamino amine is one or more in ammonia, quadrol, hexanediamine, diethylenetriamine; Described esters monomer is acrylic ester compound, and described acrylic ester compound is one or both in methyl acrylate, methyl methacrylate.
As the preferred embodiment of one, the mol ratio of described amine monomers and described esters monomer is 1:2.5, and the decomposition temperature of described amine-terminated hyperbrancedization daiamid is 268 DEG C.
As the preferred embodiment of one, the addition of described amine-terminated hyperbrancedization daiamid is 0.5-1%, and 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.
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), amine-terminated hyperbrancedization daiamid carries out drying under room temperature in vacuum drying oven, and time of drying is 5-7h.
As the preferred embodiment of one, described step 2) in, plastics and amine-terminated hyperbrancedization daiamid mix in high-speed mixer, and mixing time is 3-6min, and mixing velocity is 700-1500r/min.
As the preferred embodiment of one, in described step 4), the particle produced carries out drying in convection oven.
Beneficial effect of the present invention: the plastics such as PPC, PP, PE, PA and over-branched polyamidoamine melt blended material are prepared from by twin screw extruder by the present invention, this over-branched polyamidoamine molecule skin is containing a large amount of active function groups, and melt viscosity is lower, over-branched polyamidoamine adds the effective melt viscosity that significantly can reduce plastics in the plastics substrates such as PPC, PP, PE, PA 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, substantially increases tensile strength and the processing characteristics of the plastics such as PPC, PP, PE, PA.The tensile strength of plastics reaches 30MPa, and intensity can reach film-grade LLDPE and PVC.
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
The amine-terminated hyperbrancedization daiamid of 0.5 weight part and the PPC of 100 weight parts are mixed, extruding pelletization, dry, obtain the PPC product of modification.
embodiment two
The amine-terminated hyperbrancedization daiamid of 5 weight parts and the PPC of 100 weight parts are mixed, extruding pelletization, dry, obtain the PPC product of modification.
embodiment three
Amine-terminated hyperbrancedization daiamid is dry, for subsequent use; Get the PPC of 100 weight parts and the above-mentioned amine-terminated hyperbrancedization daiamid of 0.1 weight part, mixing, obtains mixture, 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; To produce particle, at 50 DEG C, dry 1h, obtains the PPC product of modification.
embodiment four
Amine-terminated hyperbrancedization daiamid is dry, for subsequent use; Get the PPC of 100 weight parts and the above-mentioned amine-terminated hyperbrancedization daiamid of 1 weight part, mixing, obtains mixture, 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; To produce particle, at 50 DEG C, dry 2h, obtains the PPC product of modification.
embodiment five
By amine-terminated hyperbrancedization daiamid under room temperature at the dry 5h of vacuum drying oven, be put in dry seal cavity and preserve, this material is light yellow solid or thick liquid; The over-branched polyamidoamine getting 100 weight part PPC and 0.25 weight part is put in the high-speed mixer of 1500r/min and mixes 3min, then imports 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 will produce particle and be put in dry 1h in 50 DEG C of convection oven temperature, obtain the PPC product of modification.
In the present invention, mixing velocity is the rotating speed of high-speed mixer.Here PPC plastics also can be the one in ABS, PET, PBT, PLA poly(lactic acid), PP, PE, PC, PS or PA.
embodiment six
Under ice bath, the 14Kg quadrol (EDA) being dissolved in 56Kg methyl alcohol is joined in 1 ton of reactor, 50.17Kg methyl acrylate is dissolved in 290Kg methyl alcohol, and adds in aforesaid reaction vessel, make it mix with quadrol methanol solution, obtain mixing solutions; Mixing solutions, under the protection of inert gas such as nitrogen, at room temperature, reacts 30-55h; Then, at 55-65 DEG C, carry out underpressure distillation, obtain thick product; Thick product is warmed up to 110-160 DEG C, and reaction 2-7h, obtains amine-terminated hyperbrancedization daiamid product.
Certainly, also can change into as the quadrol of amine monomers is here the mixture of a kind of, multiple in the polyamino amine such as ammonia, hexanediamine, diethylenetriamine or itself and quadrol; Methyl acrylate as esters monomer also can be the acrylic ester compounds such as methyl methacrylate, or the mixture of methyl acrylate and methyl methacrylate; The mol ratio of amine monomers and esters monomer can also be 1:1.5, and also can be 1:3.5, amine monomers and esters monomer total mass account for the 10-30% of mixing solutions total mass.
By above-mentioned amine-terminated hyperbrancedization daiamid under room temperature at the dry 7h of vacuum drying oven, be put in dry seal cavity and preserve, this material is light yellow solid or thick liquid; The over-branched polyamidoamine getting 100 weight part PPC and 0.25 weight part is put in high-speed mixer and mixes 6min; Then, import in hermetically drying hopper, for subsequent use; Twin screw extruder 5 warm areas are all heated to 160 DEG C, after preheating 1h, blanking extruding pelletization; Then, the particle produced is put in dry 2h in 50 DEG C of convection oven temperature, obtains the PPC product of modification.
embodiment seven
Amine-terminated hyperbrancedization daiamid embodiment six prepared is at the dry 5h of vacuum drying oven under room temperature, and be put in dry seal cavity and preserve, this material is light yellow solid or thick liquid; The over-branched polyamidoamine getting 100 weight part PPC and 3 weight parts is put in the high-speed mixer of 700r/min and mixes 5min; 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 dry 2h in 50 DEG C of convection oven temperature, obtains the PPC product of modification.
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 amine-terminated hyperbrancedization daiamid 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 2.30-4.01%, has good cutting performance; Its HDT raises to some extent, and namely modified PPC has better 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 declines to some extent, and namely modified PPC reduces the flowing property adding man-hour; And in the process of PPC modification, the addition of amine-terminated hyperbrancedization daiamid is few, easy to process, and cost is low.
The physicals of table 1PPC/ amine-terminated hyperbrancedization daiamid
Beneficial effect of the present invention: the plastics such as PPC, PP, PE, PA and over-branched polyamidoamine melt blended material are prepared from by twin screw extruder by the present invention, this over-branched polyamidoamine molecule skin is containing a large amount of active function groups, and melt viscosity is lower, over-branched polyamidoamine adds the effective melt viscosity that significantly can reduce plastics in the plastics substrates such as PPC, PP, PE, PA 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, substantially increases tensile strength and the processing characteristics of the plastics such as PPC, PP, PE, PA.The tensile strength of plastics reaches 30MPa, and intensity can reach film-grade LLDPE and PVC.
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 over-branched polyamidoamine in plastic working, is characterized in that:
The amine-terminated hyperbrancedization daiamid of 0.1-5 weight part and the plastics of 100 weight parts are mixed, extruding pelletization, dry, obtain the plastic prod of modification.
2. the application of over-branched polyamidoamine according to claim 1 in plastic working, is characterized in that: comprise the following steps:
1) amine-terminated hyperbrancedization daiamid is dry, for subsequent use;
2) get the amine-terminated hyperbrancedization daiamid 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 over-branched polyamidoamine according to claim 1 and 2 in plastic working, is characterized in that, the preparation method of described amine-terminated hyperbrancedization daiamid is:
A) under ice bath, the methanol solution of esters monomer is added drop-wise in the methanol solution of amine monomers, obtains mixing solutions;
B) by step a) gained mixing solutions, under protection of inert gas, at room temperature, reaction 30-55h, and underpressure distillation is carried out at 55-65 DEG C, obtain thick product;
C) by thick for step b) gained product, at 110-160 DEG C, reaction 2-7h, obtains amine-terminated hyperbrancedization daiamid product.
4. the application of over-branched polyamidoamine according to claim 3 in plastic working, is characterized in that:
The mol ratio of described amine monomers and described esters monomer is 1:1.5-3.5, and amine monomers and esters monomer total mass account for the 10-30% of mixing solutions total mass;
Described amine monomers is polyamino amine, and described polyamino amine is one or more in ammonia, quadrol, hexanediamine, diethylenetriamine;
Described esters monomer is acrylic ester compound, and described acrylic ester compound is one or both in methyl acrylate, methyl methacrylate.
5. the application of over-branched polyamidoamine according to claim 4 in plastic working, is characterized in that:
The mol ratio of described amine monomers and described esters monomer is 1:2.5, and the decomposition temperature of described amine-terminated hyperbrancedization daiamid is 268 DEG C.
6. the application of over-branched polyamidoamine according to claim 1 and 2 in plastic working, is characterized in that:
The addition of described amine-terminated hyperbrancedization daiamid is 0.5-1%, and described plastics are one or more in PPC, ABS, PET, PBT, PLA poly(lactic acid), PP, PE, PC, PS or PA.
7. the application of over-branched polyamidoamine 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.
8. the application of over-branched polyamidoamine according to claim 7 in plastic working, is characterized in that:
In described step 1), amine-terminated hyperbrancedization daiamid carries out drying under room temperature in vacuum drying oven, and time of drying is 5-7h.
9. the application of over-branched polyamidoamine according to claim 8 in plastic working, is characterized in that:
Described step 2) in, plastics and amine-terminated hyperbrancedization daiamid mix in high-speed mixer, and mixing time is 3-6min, and mixing velocity is 700-1500r/min.
10. the application of over-branched polyamidoamine according to claim 9 in plastic working, is characterized in that:
In described step 4), the particle produced carries out drying in convection oven.
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Cited By (10)
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| CN105964227A (en) * | 2016-05-06 | 2016-09-28 | 福州大学 | Hyperbranched polyamide-grafted chitosan adsorbent and its preparation method and use |
| CN106674966A (en) * | 2016-12-27 | 2017-05-17 | 上海普利特化工新材料有限公司 | Low-shrinkage rate and high-fluidity type fiber-reinforced PC (polycarbonate) and ABS (acrylonitrile-butadiene-styrene) alloy material and preparation method thereof |
| CN106674746A (en) * | 2016-12-29 | 2017-05-17 | 上海普利特复合材料股份有限公司 | Polypropylene (PP) continuous long fiber sheet and preparation method thereof |
| CN106977911A (en) * | 2017-03-16 | 2017-07-25 | 广东圆融新材料有限公司 | A kind of high-gloss scraping-resistant daiamid composition and preparation method thereof |
| CN108239340A (en) * | 2018-01-08 | 2018-07-03 | 上海金发科技发展有限公司 | The polypropylene of a kind of damage resistant/end amido branched polymeric compositions and preparation method thereof |
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| CN110591223A (en) * | 2019-08-13 | 2019-12-20 | 金发科技股份有限公司 | High-filling thermoplastic resin composite material and preparation method thereof |
| CN110951166A (en) * | 2018-09-26 | 2020-04-03 | 合肥杰事杰新材料股份有限公司 | High-performance polypropylene material and preparation method thereof |
| CN115160771A (en) * | 2022-06-30 | 2022-10-11 | 宁波坚锋新材料有限公司 | Isomeric micro-crosslinked regenerated nylon and preparation method thereof |
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