CN115772320A - Nucleating agent master batch, foaming material and preparation method thereof - Google Patents
Nucleating agent master batch, foaming material and preparation method thereof Download PDFInfo
- Publication number
- CN115772320A CN115772320A CN202211543350.3A CN202211543350A CN115772320A CN 115772320 A CN115772320 A CN 115772320A CN 202211543350 A CN202211543350 A CN 202211543350A CN 115772320 A CN115772320 A CN 115772320A
- Authority
- CN
- China
- Prior art keywords
- parts
- nucleating agent
- antioxidant
- master batch
- weight
- 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
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 99
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 82
- 238000005187 foaming Methods 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 38
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 30
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 30
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000006260 foam Substances 0.000 claims abstract description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 68
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002861 polymer material Substances 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010899 nucleation Methods 0.000 abstract description 24
- 230000006911 nucleation Effects 0.000 abstract description 24
- 238000002425 crystallisation Methods 0.000 abstract description 18
- 230000008025 crystallization Effects 0.000 abstract description 18
- 239000011148 porous material Substances 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 10
- 210000004027 cell Anatomy 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000006261 foam material Substances 0.000 description 6
- 210000000497 foam cell Anatomy 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a nucleating agent master batch, a foaming material and a preparation method thereof. The nucleating agent master batch comprises the following components in parts by weight: 100 parts of a polymer matrix; 0.5-3 parts of graphite; 0.5-2 parts of metal oxide; 0.5-2 parts of polydimethylsiloxane; 0.5-3 parts of antioxidant. The nucleating agent master batch provided by the invention can promote polymer crystallization in the polymer foaming process, improve the foaming nucleation density, reduce the diameter of foam pores and improve the uniformity of pore size distribution.
Description
Technical Field
The invention relates to a nucleating agent master batch, a foaming material and a preparation method thereof.
Background
The polymer foam material is a microporous material having a polymer as a matrix and containing a large number of bubbles therein. The polymer foam product has the characteristics of light weight, material saving, sound and heat insulation, high specific strength, excellent buffering performance and the like. Compared with the traditional foam material, the PET foam material has more excellent properties, such as good high-temperature stability, excellent mechanical property, fatigue resistance, high compression strength and shear strength, complete recovery and the like. Besides the application in the aspects of conventional food packaging, building materials and the like, the low-density PET composite structure material can keep higher strength and rigidity on the premise of not increasing the weight of the product, and has wide application prospect in the fields of wind power, rail traffic, ships and naval vessels, aerospace and the like. However, ester groups and benzene rings in the PET molecular chain form a conjugated system, and as a whole, when the chain segment freely rotates around the rigid group, the rotation energy resistance is large, and the whole PET molecular chain is rigid. The rigid conjugated structure hinders the movement of the molecular chain segment and reduces the movement activity of the molecular chain segment, so that the defects of slow crystallization rate, high mold temperature, long molding period, poor dimensional stability and the like exist in the processing process of PET. The PET foam has the problems of wide pore size distribution of cells, easy breakage of cells in a foaming process, low cell nucleation density, irregular cell morphology and the like, and the problems can seriously influence and limit the application of the PET foam material.
Researchers usually make PET foam cells more regular by adding a foaming nucleating agent during modification, and improve the nucleation density. The commonly used foaming nucleating agent mainly comprises inorganic fillers such as talcum powder, montmorillonite, various calcium salts and magnesium salts, and the like, or organic acid and derivatives thereof, and the action principle of the commonly used foaming nucleating agent is mainly to promote heterogeneous nucleation during foaming. The commonly used crystal nucleating agents include inorganic type nucleating agents, organic small molecule type nucleating agents and organic high molecule type nucleating agents. The existing nucleating agent researches only pay attention to crystallization conditions or foaming conditions, and no or fresh patents which simultaneously promote crystallization and promote foaming nucleation exist. For example: the Chinese invention patent with the publication number of CN109749370A discloses a crystallization nucleating agent compounded by a carboxylate nucleating agent and other components, but the carboxylate reacts with a PET molecular chain to cause chain breakage, which reduces the foamability of PET. Pangwan, jin Yimin, in samyin ([ Pangwan, jin Yimin, in samyin. The effect of metal carboxylate nucleating additives on PET crystal nucleation and molecular weight [ J ] Polymer Material science and engineering, 1989, 74-80 ]) studies also demonstrated that sodium carboxylates can break the chain of PET, reducing molecular weight. This is disadvantageous for the modification of PET and for the use in foaming.
At present, in the foaming aspect of polymer materials, research points of related researchers are mainly focused on modification of polymers, and research on foaming nucleating agents is relatively deficient, so that the types of the existing industrialized nucleating agents are single, the universality is poor, the nucleating effect is poor, the nucleating master batch with good effect depends on import, and the cost is high.
Therefore, aiming at the problems of slow crystallization rate of polymer foaming material, uneven foam cell size of the foaming material, low nucleation density and the like, the development of the compound foaming nucleating agent master batch capable of being industrially produced has great commercial value in the field, and is a problem to be solved in the field.
Disclosure of Invention
The invention mainly aims to overcome the defects of slow crystallization rate, nonuniform foam pores and low nucleation density of the foaming material in the prior art, and provides a nucleating agent master batch, the foaming material and a preparation method thereof. The nucleating agent master batch provided by the invention can promote polymer crystallization in the polymer foaming process, improve the foaming nucleation density, reduce the diameter of foam pores and improve the uniformity of pore size distribution.
The invention takes polymer with a net structure as a dispersion carrier, graphite, metal oxide particles and polydimethylsiloxane as nucleating agents, and prepares the nucleating agent master batch by melt blending. The master batch is applied to a small amount of polymer foaming process, can obviously improve crystallization rate, can obviously improve the cell density of the foaming material after foaming, reduce cell diameter and cell diameter distribution, simultaneously can not influence the rheological property of the polymer, and the prepared product is stable, uniform and smooth.
Further analysis and research show that the reason is probably that the lamellar structure in the microstructure of the graphite can pre-arrange the molecular chains of the polymer to be foamed on the surface of the polymer to be foamed, so that the molecular chains have the function of promoting crystallization and nucleation, and the planar structure of the molecular chains can reduce Gibbs free energy of foaming and nucleation in the foaming process and promote the foaming and nucleation. Meanwhile, the metal oxide can promote heterogeneous nucleation during foaming while promoting crystallization, and the polydimethylsiloxane has a lubricating effect, can increase the movement capacity of polymer molecular chains, promotes crystallization, and is used as a third phase component to promote heterogeneous nucleation during foaming. The functions of the components are combined to generate excellent synergistic effect, and finally the excellent effect of the invention is realized.
The invention provides a nucleating agent master batch which comprises the following components in parts by weight:
100 parts of a polymer matrix;
0.5-3 parts of graphite;
0.5-2 parts of metal oxide;
0.5-2 parts of polydimethylsiloxane;
0.5-3 parts of antioxidant.
In the present invention, the polymer matrix may be a polymer conventionally used in the art for preparing foamed materials; preferably a polyester resin such as polyethylene terephthalate.
In the present invention, the polymer matrix preferably has a network structure.
When the polymer matrix is polyethylene terephthalate (PET), the polyethylene terephthalate may satisfy at least one of the following conditions:
(1) the intrinsic viscosity of the polyethylene glycol terephthalate is 0.6-1.0dl/g;
(2) the weight average molecular weight of the polyethylene terephthalate is 3.0 multiplied by 10 3 -8.0×10 4 ；
(3) The polyethylene terephthalate has a number average molecular weight of 2.0X 10 3 -7.0×10 4 。
In the present invention, the graphite is generally in a powder form; preferably flake nano graphite powder; the thickness of the flaky nano graphite powder is preferably less than 80nm, for example, less than 40nm; the flake nano graphite powder preferably has a flake diameter of 1 to 10 μm, for example, 3 to 6 μm.
In the present invention, the metal oxide is preferably a transition metal oxide; preferably zirconium oxide and/or zinc oxide.
In the present invention, the particle size of the metal oxide is preferably on the order of nanometers; more preferably 20-50nm, such as 20-40nm or 30-50nm.
In the present invention, the polydimethylsiloxane may be conventional in the art, and preferably may have a weight average molecular weight of 770 to 4000, for example 2000.
In the present invention, the antioxidant generally refers to an antioxidant capable of preventing the polymer from degrading, preferably an amine antioxidant, a phenol antioxidant or a complex antioxidant; the amine antioxidant is more preferably antioxidant 405; the phenolic antioxidant is more preferably an antioxidant 1010; the composite antioxidant is more preferably antioxidant B225.
In the present invention, the nucleating agent masterbatch preferably further includes silicon dioxide. The addition of the silica can result in a foamed material with narrower pore size distribution, better size uniformity and faster crystallization rate.
Wherein, the silicon dioxide is preferably 0 to 3 parts by weight but not 0; more preferably 0.5 to 2 parts.
Wherein, the silicon dioxide is preferably hydrophobic nano silicon dioxide.
Wherein the particle diameter D50 of the silica is more preferably 20 to 60nm.
In the present invention, the weight part of the graphite may be 1 to 2.5 parts, for example, 1.5 parts.
In the present invention, the metal oxide may be present in an amount of 0.5 to 1.5 parts by weight, for example 1 part by weight.
In the present invention, the part by weight of the polydimethylsiloxane may be 0.5 to 1.5 parts, for example, 1 part.
In the present invention, the antioxidant may be present in an amount of 0.5 to 1.5 parts by weight, for example 1 part by weight.
In the invention, the weight ratio of the polymer matrix, the graphite, the metal oxide, the polydimethylsiloxane and the antioxidant can be 100 (1-2.5): 0.5-1.5.
In some embodiments, the nucleating agent masterbatch comprises the following components in parts by weight: 100 parts of PET resin, 1010 parts of antioxidant, 1 part of nano zirconia, 1.5 parts of graphite, 0.5 part of silicon dioxide and 1 part of polydimethylsiloxane.
In some specific embodiments, the nucleating agent masterbatch comprises the following components in parts by weight: 100 parts of PET resin, 0.5 part of antioxidant 1010, 0.5 part of nano zirconia, 0.5 part of graphite, 0.5 part of silicon dioxide and 0.5 part of polydimethylsiloxane.
In some specific embodiments, the nucleating agent masterbatch comprises the following components in parts by weight: 100 parts of PET resin, 1010 parts of antioxidant, 2 parts of nano zirconia, 3 parts of graphite, 0.5 part of silicon dioxide and 2 parts of polydimethylsiloxane.
The invention also provides a preparation method of the nucleating agent master batch, which comprises the following steps: and extruding and granulating the components of the nucleating agent master batch to obtain the nucleating agent.
In the present invention, the polymer matrix is preferably further subjected to a heating pretreatment before the extrusion granulation, and the heating pretreatment is, for example, drying by a blast oven and then transferring to a vacuum oven for drying.
Wherein the drying temperature may be 120 ℃; the drying time may be 8 to 12 hours.
Wherein the drying temperature can be 120 ℃; the drying time period can be 8-12 hours.
In the present invention, the graphite, the metal oxide, the polydimethylsiloxane and the antioxidant are preferably further subjected to a heating pretreatment before the extrusion granulation, and the heating pretreatment is preferably vacuum oven drying.
Wherein the drying temperature can be 80 ℃; the drying time period can be 8-12 hours.
In the present invention, the extrusion granulation is preferably performed by adding a mixture of the components of the nucleating agent masterbatch into a twin-screw extruder, melting and blending, extruding, and drying. The double-screw extruder has low energy consumption and easy operation, and is beneficial to large-scale continuous production.
Wherein the temperature of the working area of the double-screw extruder can be 180-275 ℃; the working area is preferably divided into five zones, the temperatures being: the first zone is 180-200 deg.C, the second zone is 255-265 deg.C, the third zone is 260-270 deg.C, the fourth zone is 265-275 deg.C, and the fifth zone is 265-275 deg.C.
Wherein the die temperature of the twin-screw extruder may be 265 to 275 ℃, e.g., 270 ℃.
Wherein the screw speed of the twin-screw extruder may be 220-270rpm, for example 240rpm.
The invention also provides the nucleating agent master batch prepared by the preparation method.
The invention also provides a nucleating agent master batch, which comprises a continuous phase and a disperse phase; the continuous phase comprises a polymer matrix, and the polymer matrix is a reticular structure; the dispersed phase comprises graphite, metal oxide, polydimethylsiloxane and antioxidant; wherein, the nucleating agent master batch comprises 100 parts of the polymer matrix, 0.5-3 parts of graphite, 0.5-2 parts of metal oxide, 0.5-2 parts of polydimethylsiloxane and 0.5-3 parts of antioxidant by weight.
In the present invention, the shape of the nucleating agent master batch is not particularly limited, and is preferably rod-shaped; the diameter of the rod-shaped nucleating agent master batch is more preferably 0.1mm-5mm; the length of the rod-like nucleating agent master batch is more preferably 3mm to 10mm. The diameter is the diameter when the shape of the nucleating agent master batch is a rod, and the length is the length when the shape of the nucleating agent master batch is a rod.
In the present invention, the continuous phase and the dispersed phase may be in the meaning conventionally understood in the art, i.e., the graphite, the oxide, the polydimethylsiloxane, and the antioxidant are dispersed as a dispersed phase in the polymer matrix of the continuous phase.
In the present invention, said polymer matrix, said graphite, said metal oxide, said polydimethylsiloxane and said antioxidant are preferably as described above.
The graphite and the metal oxide in the nucleating agent master batch can meet the requirement of lower addition amount in the range and can obtain good effect. And because graphite and metal oxide are nanoparticles, the agglomeration is easy to occur, the foaming is influenced, the agglomeration can be effectively avoided due to the lower addition amount, the dispersion effect is improved, and the rheological property of the polymer cannot be influenced due to the addition of the nucleating agent master batch, so that the cell size of the foaming material is more uniform.
The invention also provides a preparation method of the foaming material, which comprises the following steps: and granulating the mixture of the polymer material to be foamed and the nucleating agent master batch, and then foaming.
In the present invention, the mixture is preferably further subjected to a heating pretreatment before being granulated, wherein the heating pretreatment is, for example, drying by a blast oven and then transferring to a vacuum oven for drying.
Wherein the drying temperature can be 80-120 ℃; the drying time may be 8 to 12 hours.
Wherein the drying temperature can be 80-120 ℃; the drying time period may be 8 to 12 hours.
In the present invention, the mixture preferably further comprises an epoxy chain extender and an antioxidant.
In the present invention, the polymer material to be foamed is preferably the same as the polymer matrix in the nucleating agent masterbatch, and the polymer material to be foamed is preferably polyethylene terephthalate.
In the present invention, the granulation may be conventional in the art, and is preferably performed by adding a mixture of the polymer material to be foamed and the nucleating agent masterbatch into a twin-screw extruder for melt blending, followed by extrusion and drying.
Wherein the temperature of the working zone of the twin-screw extruder can be 180-275 ℃; the working area is preferably divided into five zones, the temperatures being: the first zone is 185-200 deg.C, the second zone is 255-265 deg.C, the third zone is 260-270 deg.C, the fourth zone is 265-275 deg.C, and the fifth zone is 265-275 deg.C.
Wherein the die temperature of the twin-screw extruder may be 265 to 275 ℃, e.g., 270 ℃.
Wherein the screw speed of the twin-screw extruder may be 240-300rpm, for example 280rpm.
In the present invention, the foaming process may be conventional in the art, and preferably the mixture of the granulated foaming material and the foaming agent is sequentially subjected to temperature rise, temperature reduction, temperature preservation and pressure reduction.
Wherein the temperature of the temperature rise and the heat preservation is preferably 260-270 ℃, such as 265 ℃; the temperature rise and heat preservation refers to maintaining for a certain time at the temperature until the foaming raw material is completely melted and the foaming agent is completely saturated in the foaming raw material.
Wherein the pressure for raising and maintaining the temperature is preferably 12-18MPa, such as 15MPa.
Wherein the temperature of the temperature reduction and heat preservation is 240-250 ℃, such as 245 ℃; the temperature reduction and heat preservation refers to maintaining for a certain time until the foaming raw material and the foaming agent reach a new equilibrium state.
Wherein, the pressure reduction is preferably reduced to normal pressure to induce the nucleation and growth of the foam cells. The atmospheric pressure may be conventional in the art and is typically 0.1MPa.
Wherein the rate of said depressurization is preferably 200-400MPa/s, such as 300MPa/s.
In the invention, the addition amount of the nucleating agent master batch can be 1-12%, preferably 1-5%, and the percentage is the mass of the nucleating agent master batch accounting for the mass of the polymer material to be foamed.
In the present invention, the foaming agent used for the foaming may be conventional in the art, and for example, includes one or more of cyclopentane, supercritical carbon dioxide, and supercritical nitrogen.
The invention also provides a foaming material prepared by the preparation method.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the polymer with a net structure is used as a matrix, and graphite, metal oxide and polydimethylsiloxane are dispersed in the matrix to form the nucleating agent master batch, so that the components can be pre-dispersed, the components are dispersed more uniformly, and agglomeration is avoided. Meanwhile, the components are mutually matched and have synergistic effect, so that the nucleating agent master batch is applied to the foaming process of the polymer, the crystallization rate of the polymer can be improved, the nucleation density of the obtained foaming material can be improved, the diameter of cells is obviously reduced, the uniformity of the diameter distribution of the cells is improved, and the size of the cells is more uniform and regular.
Drawings
FIG. 1 is a scanning electron microscope image of cells of the foamed material of application example 1.
FIG. 2 is a scanning electron microscope image of the cells of the foamed material of application example 2.
FIG. 3 is a scanning electron microscope image of the cells of the foamed material of application example 3.
FIG. 4 is a scanning electron microscope image of the cells of the foamed material of application example 4.
FIG. 5 is a scanning electron microscope image of the cells of the foamed material of application example 5.
FIG. 6 is a scanning electron microscope photograph of cells of the foamed material of application example 6.
FIG. 7 is a scanning electron microscope photograph of cells of the foamed material of comparative example 1.
FIG. 8 is a scanning electron microscope photograph of cells of the foamed material of comparative example 2.
FIG. 9 is a DSC temperature drop curve of the PET resin raw material used in application example 1 and the modified PET resin foaming raw material obtained in step (1).
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
In the following examples, application examples and comparative examples, PET resin was purchased from Jiangsu three-alley group, inc. under the product designation CZ-318;
in the following examples, epoxy chain extenders were used
4368 acrylate polymers (functionality 9, epoxy equivalent weight 285 g/mol) were purchased from basf, ltd, germany;
the antioxidant 1010 is pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], which is purchased from Chiloei (Shanghai) chemical industry development Co., ltd.;
the nano zirconia (product brand is XFI 01) and the graphite (product brand is XF 011) are purchased from Nanjing Xiancheng nano material Co., ltd;
polydimethylsiloxane (molecular weight 2000) was purchased from alfa aesar (china) chemical ltd;
silica was purchased from Shanghai Aladdin Biotechnology Ltd.
Example 1: the nucleating agent master batch 1 is prepared by the following processing processes:
blowing and drying commercially available PET resin for 12 hours at 120 ℃, and then drying the PET resin for 12 hours in vacuum at 120 ℃; carrying out vacuum drying on the antioxidant 1010, the nano zirconia, the graphite and the silicon dioxide at the temperature of 80 ℃ for 12 hours, and fully premixing in parts by mass as follows:
100 parts of PET resin
Antioxidant 1010 parts
1 part of nano zirconia
1.5 parts of graphite
0.5 part of silicon dioxide
1 part of polydimethylsiloxane
And adding the fully premixed materials into a double-screw extruder with the rotating speed of 240rpm, the first zone of 180 ℃, the second zone of 260 ℃, the third zone of 265 ℃, the fourth zone of 270 ℃, the fifth zone of 275 ℃ and the die head of 275 ℃ for melt blending, granulating an extrudate, and fully drying to obtain the nucleating agent master batch 1.
Example 2
The difference between this example and example 1 is only that the content of each component is different, and the pretreatment method and the extrusion granulation process are the same as those of example 1, and the nucleating agent master batch 2 is prepared.
The composition comprises the following components in parts by mass:
100 parts of PET resin
0.5 part of antioxidant 1010
0.5 part of nano zirconia
0.5 part of graphite
5 portions of silicon dioxide
0.5 part of polydimethylsiloxane.
Example 3
The difference between this example and example 1 is only that the content of each component is different, the pretreatment method and the extrusion granulation process are the same as those of example 1, and the nucleating agent master batch 3 is prepared
The composition comprises the following components in parts by mass:
100 parts of PET resin
Antioxidant 1010 parts
2 portions of nano zirconia
3 parts of graphite
0.5 part of silicon dioxide
2 parts of polydimethylsiloxane.
The nucleating agent master batches prepared in the embodiments 1 to 3 of the invention are all rod-shaped, the diameter of the nucleating agent master batches is within the range of 0.1mm to 5mm, and the length of the nucleating agent master batches is within the range of 3mm to 10mm.
Application example 1
(1) Carrying out forced air drying on commercially available PET resin and nucleating agent master batch 1 at 120 ℃ for 12 hours, and then carrying out vacuum drying at 120 ℃ for 12 hours; the antioxidant 1010 is dried in vacuum for 12 hours at the temperature of 80 ℃; fully premixing PET resin, nucleating agent master batch 1, epoxy chain extender and antioxidant 1010 in parts by mass as follows:
100 parts of PET resin
1 part of nucleating agent master batch
Epoxy chain extender 1 part
0.5 part of antioxidant 1010
Adding the fully premixed materials into a double-screw extruder with the rotating speed of 280rpm, the first zone of 185 ℃, the second zone of 265 ℃, the third zone of 270 ℃, the fourth zone of 275 ℃, the fifth zone of 275 ℃ and the die head of 275 ℃ for melt blending, granulating the reaction extrudate, tabletting and drying to obtain a modified PET resin foaming raw material;
(2) Placing the modified PET resin foaming raw material into a high-pressure kettle and sealing; followed by low pressure CO 2 Purging the autoclave for 3 times to completely replace air in the autoclave, heating the autoclave to 265 ℃, boosting the temperature to 15MPa, and preserving the temperature for 30 minutes to ensure the complete melting of the modified PET resin foaming raw material and CO 2 Complete saturation in the modified PET resin foaming raw material; then cooling to 245 ℃, and preserving heat for 20 minutes to reach a new equilibrium state; and (3) instantly reducing the pressure in the kettle to normal pressure at the speed of 300MPa/s through a pressure reduction control valve to induce the nucleation and growth of foam cells, thus obtaining the PET foam material.
(3) Cooling the PET foaming material to 0 ℃, quenching, and scanning and analyzing the quenched section.
Application example 2
The difference between the application example and the application example 1 is that the temperature is reduced to 240 ℃ in the foaming process, and other conditions are the same.
Application example 3
The difference between the application example and the application example 1 is only that the nucleating agent master batch 1 is replaced by the nucleating agent master batch 2, and other conditions are the same.
Application example 4
The difference between the application example and the application example 1 is only that the nucleating agent master batch 1 is replaced by the nucleating agent master batch 2, the temperature is reduced to 240 ℃ in the foaming process, and other conditions are the same.
Application example 5
The difference between the application example and the application example 1 is only that the nucleating agent master batch 1 is replaced by the nucleating agent master batch 3, and other conditions are the same.
Application example 6
The difference between the application example and the application example 1 is only that the nucleating agent master batch 1 is replaced by the nucleating agent master batch 2, the temperature is reduced to 240 ℃ in the foaming process, and other conditions are the same.
Comparative example 1
Drying commercially available PET resin by blowing at 120 ℃ for 12 hours, and then drying in vacuum at 120 ℃ for 12 hours; the antioxidant 1010 is dried in vacuum for 12 hours at the temperature of 80 ℃; fully premixing PET resin, an epoxy chain extender and an antioxidant 1010 in parts by weight as follows:
100 parts of PET resin
Epoxy chain extender 1 part
0.5 part of antioxidant 1010
And adding the fully premixed materials into a double-screw extruder with the rotating speed of 280rpm, the first zone of 185 ℃, the second zone of 265 ℃, the third zone of 270 ℃, the fourth zone of 275 ℃, the fifth zone of 275 ℃ and the die head of 275 ℃, carrying out melt blending, granulating a reaction extrudate, tabletting and drying to obtain the PET resin foaming raw material.
The above PET resin foaming raw material was placed in an autoclave and sealed, followed by low-pressure CO 2 Purging the autoclave for 3 times to completely replace air in the autoclave, heating the autoclave to 265 ℃, boosting the temperature to 15MPa, and preserving the temperature for 30 minutes to ensure the complete melting of the PET resin foaming raw material and CO 2 Complete saturation in the PET resin foam stock; then the temperature is reduced to 245 ℃, and the temperature is preserved for 20 minutes to reach a new equilibrium state. The pressure in the kettle is instantaneously reduced to normal pressure at the speed of 300MPa/s through a pressure reduction control valve so as to induce the nucleation and growth of foam cells. And cooling the foaming sample to 0 ℃, quenching, and scanning and analyzing the quenched section of the foaming sample.
Comparative example 2
The present comparative example differs from comparative example 1 only in that the temperature is lowered to 240 ℃.
Effect example 1
(1) Differential scanning calorimetry
And analyzing the modified PET material before and after the nucleating agent is added by adopting a Differential Scanning Calorimeter (DSC) to investigate the promoting effect of the nucleating agent on the material crystallization. The analyzer is a NETZSCH 200F3 differential scanning calorimeter of the german navy company, and the result is shown in fig. 9 (wherein the PET resin raw material is commercially available PET resin), it can be seen that the temperature corresponding to the peak value of the modified PET resin foaming raw material curve is increased by approximately 30 ℃ compared with the PET resin raw material, which indicates that the sample can start to crystallize at a higher temperature, the nucleating agent master batch has an obvious promoting effect, and the continuous industrial production and material demoulding are facilitated; moreover, the curve peak of the material added with the nucleating agent master batch is sharper, and the narrower and sharper the peak is, the faster the crystallization rate is; moreover, the peak area of the material added with the nucleating agent master batch is larger, which shows that the crystallinity is higher at the cooling rate.
(2) Analysis by scanning Electron microscope
A section of a sample of the foamed polymer material was analyzed using a Scanning Electron Microscope (SEM) to examine the cell density and the cell size of the foamed polymer material. The analytical instrument is a JSM-6360LV type scanning electron microscope of JOEL company in Japan.
The pore size range and nucleation density of the foam can be analyzed from the SEM photograph. Counting the number n (> 100) of micropores from the SEM photograph, and determining the area (cm) of the photograph 2 )，ρ 0 Density of the unfoamed sample, p f For the density of the foamed sample, the nucleation density was estimated using the following formula, and the calculation results are shown in table 1:
fig. 1, fig. 2, fig. 3, fig. 4, fig. 5, and fig. 6 are SEM images of the foamed materials obtained in application examples 1 to 6, and it can be seen from fig. 1 to 6 that the PET foamed material added with the nucleating agent masterbatch has narrow and uniform cell distribution, high nucleation density, and remarkable cubic feature of cell morphology.
FIGS. 7 and 8 are SEM images of the foams obtained in comparative examples and 2, respectively, and it can be seen that the foams obtained without adding the nucleating agent master batch have wide cell distribution, large size-hole difference, low nucleation density and irregular cell morphology.
(3) Method for testing foaming multiplying power
The densities of the PET resin raw material and the PET foamed material in application examples 1 to 6 and comparative examples 1 to 2 were measured, respectively, and the foaming ratio was calculated, and the calculation results are shown in Table 1.
The method of calculating the expansion ratio is shown in (1):
R v ＝P unfoamed /P foamed (1)
wherein P is unfoamed And P foamed The densities of the PET resin raw material and the PET foam material are respectively. The density was measured by an electronic densitometer, available from Fobus, inc., xiamen, and was FK-100E.
TABLE 1
| Pore diameter | Difference in pore diameter | Nucleation density | Expansion ratio | |
| Application example 1 | 4.5～16.0μm | 11.5 | 1.97×10 10 Per cm 3 | 16 times of |
| Application example 2 | 3～15μm | 12 | 2.9×10 10 Per cm 3 | 14 times of |
| Application example 3 | 12～30μm | 18 | 1.02×10 9 Per cm 3 | 29 times of |
| Application example 4 | 8～21μm | 13 | 4.62×10 9 Per cm 3 | 27 times of |
| Application example 5 | 3～10μm | 7 | 5.2×10 10 Per cm 3 | 11 times of |
| Application example 6 | 2～8μm | 6 | 8.04×10 10 Per cm 3 | 10 times of |
| Comparative example 1 | 15～65μm | 50 | 7.2×10 8 Per cm 3 | 23 times of |
| Comparative example 2 | 10～40μm | 30 | 1.67×10 9 Per cm 3 | 16 times of |
Note: the pore size difference is obtained from the maximum value minus the minimum value of the pore size range, as in application example 1 with 16.0-4.5= 11.5.
It can be clearly seen from table 1 that the pore size distribution and the difference of the foamed material prepared in the application example are smaller than those of the comparative examples, which indicates that the foamed material prepared by adding the nucleating agent masterbatch has uniform pore size and high nucleation density, indicates that the foamed material has uniform structure, and can uniformly disperse external force when being subjected to external pressure, thereby obtaining higher structural stability. Meanwhile, the crystallization promoting effect of the nucleating agent master batch can also act together with uniformly distributed holes, so that the mechanical property of the material is improved, and the industrial production and use are facilitated.
The nucleating agent master batch is prepared by pre-dispersing the nucleating agent components in the polymer matrix, and the functions of the components are utilized to be matched with each other in the polymer foaming process, so that the excellent effects of improving the crystallization rate of the polymer, improving the cell density of the foaming material, reducing the cell diameter and reducing the cell diameter distribution are realized, the method plays an important role in the preparation process of the polymer foaming material, and particularly obtains a more obvious foaming effect aiming at the PET foaming material.
Claims (10)
1. The nucleating agent master batch is characterized by comprising the following components in parts by weight:
100 parts of a polymer matrix;
0.5-3 parts of graphite;
0.5-2 parts of metal oxide;
0.5-2 parts of polydimethylsiloxane;
0.5-3 parts of antioxidant.
2. The nucleating agent masterbatch according to claim 1, wherein said polymer matrix is a polyester resin such as polyethylene terephthalate;
when the polymer matrix is polyethylene terephthalate, the polyethylene terephthalate satisfies at least one of the following conditions:
(1) the intrinsic viscosity of the polyethylene terephthalate is 0.6-1.0dl/g;
(2) the weight average molecular weight of the polyethylene terephthalate is 3.0 multiplied by 10 3 -8.0×10 4 ；
(3) The polyethylene terephthalate has a number average molecular weight of 2.0X 10 3 -7.0×10 4 ；
And/or, the polymer matrix has a network structure;
and/or the graphite is flake nano graphite powder; the thickness of the flaky nano graphite powder is preferably less than 80nm, for example, less than 40nm; the flake diameter of the flake nano graphite powder is preferably 1 to 10 μm, for example, 3 to 6 μm;
and/or, the metal oxide is a transition metal oxide; preferably zirconium oxide and/or zinc oxide;
and/or the particle size of the metal oxide is 20-50nm, such as 20-40nm or 30-50nm;
and/or the polydimethylsiloxane has a weight average molecular weight of 770 to 4000, e.g., 2000;
and/or the antioxidant is an amine antioxidant, a phenol antioxidant or a composite antioxidant; the amine antioxidant is preferably antioxidant 405; the phenolic antioxidant is preferably an antioxidant 1010; the composite antioxidant is preferably antioxidant B225;
and/or, the nucleating agent master batch also comprises silicon dioxide; the silicon dioxide is preferably hydrophobic nano silicon dioxide; the particle diameter D50 of the silica is more preferably 20 to 60nm; wherein, the silicon dioxide is preferably 0 to 3 parts by weight but not 0; more preferably 0.5 to 2 parts.
3. The nucleating agent masterbatch according to claim 1, wherein the graphite is present in an amount of 1 to 2.5 parts by weight, for example 1.5 parts;
and/or the metal oxide is present in an amount of 0.5 to 1.5 parts, for example 1 part;
and/or the polydimethylsiloxane is present in an amount of 0.5 to 1.5 parts by weight, for example 1 part;
and/or the antioxidant is 0.5-1.5 parts by weight, such as 1 part by weight;
and/or the weight ratio of the polymer matrix, the graphite, the metal oxide, the polydimethylsiloxane and the antioxidant is 100 (1-2.5): 0.5-1.5);
or the nucleating agent master batch comprises the following components in parts by weight: 100 parts of PET resin, 1010 parts of antioxidant, 1 part of nano zirconia, 1.5 parts of graphite, 0.5 part of silicon dioxide and 1 part of polydimethylsiloxane;
or the nucleating agent master batch comprises the following components in parts by weight: 100 parts of PET resin, 0.5 part of antioxidant 1010, 0.5 part of nano zirconia, 0.5 part of graphite, 0.5 part of silicon dioxide and 0.5 part of polydimethylsiloxane;
or the nucleating agent master batch comprises the following components in parts by weight: 100 parts of PET resin, 1010 parts of antioxidant, 2 parts of nano zirconia, 3 parts of graphite, 0.5 part of silicon dioxide and 2 parts of polydimethylsiloxane.
4. A method for preparing the nucleating agent masterbatch according to any one of claims 1 to 3, characterized by comprising the steps of: extruding and granulating the components of the nucleating agent masterbatch of any one of claims 1 to 3.
5. The method for preparing the nucleating agent masterbatch according to claim 4, wherein the polymer matrix is further subjected to a heating pretreatment before the extrusion granulation, and the heating pretreatment is, for example, drying by a blast oven and then transferring to a vacuum oven for drying; wherein the drying temperature is preferably 120 ℃; the drying time is preferably 8 to 12 hours; the drying temperature is preferably 120 ℃; the drying time is preferably 8-12 hours;
and/or the graphite, the metal oxide, the polydimethylsiloxane and the antioxidant are further subjected to a heating pretreatment before the extrusion granulation, wherein the heating pretreatment is preferably vacuum oven drying; wherein, the drying temperature is preferably 80 ℃; the drying time is preferably 8-12 hours;
and/or the extrusion granulation is to add the mixture of the components of the nucleating agent master batch into a double-screw extruder for melt blending, and then extrude and dry the mixture;
wherein the temperature of the working zone of the twin-screw extruder is preferably 180-275 ℃; the working area is preferably divided into five zones, the temperatures being: the first zone is 180-200 ℃, the second zone is 255-265 ℃, the third zone is 260-270 ℃, the fourth zone is 265-275 ℃ and the fifth zone is 265-275 ℃;
wherein the die temperature of the twin-screw extruder is preferably 265 to 275 ℃, for example 270 ℃;
wherein the screw rotation speed of the twin-screw extruder is preferably 220 to 270rpm, for example 240rpm.
6. A nucleating agent masterbatch, characterized in that it is produced by the method for producing the nucleating agent masterbatch according to claim 4 or 5.
7. The nucleating agent masterbatch according to any one of claims 1 to 3 and 6, comprising a continuous phase and a dispersed phase; the continuous phase comprises a polymer matrix, and the polymer matrix is a reticular structure; the dispersed phase comprises graphite, metal oxide, polydimethylsiloxane and antioxidant; wherein, the nucleating agent master batch comprises 100 parts of the polymer matrix, 0.5-3 parts of graphite, 0.5-2 parts of metal oxide, 0.5-2 parts of polydimethylsiloxane and 0.5-3 parts of antioxidant by weight, wherein the shape of the nucleating agent master batch is preferably rod-shaped; the diameter of the rod-shaped nucleating agent master batch is more preferably 0.1mm-5mm; the length of the rod-like nucleating agent master batch is more preferably 3mm to 10mm.
8. The preparation method of the foaming material is characterized by comprising the following steps: granulating and then re-foaming a mixture of the polymeric material to be foamed and the nucleating agent masterbatch according to any one of claims 1 to 3, 6 and 7.
9. The method of preparing a foam of claim 8, wherein the mixture further comprises an epoxy chain extender and an antioxidant;
and/or the addition amount of the nucleating agent master batch is 1-12%, preferably 1-5%;
and/or heating pretreatment is carried out before the mixture is granulated, wherein the heating pretreatment is to dry the mixture by a blast oven and then transfer the mixture to a vacuum oven for drying; wherein, the drying temperature is preferably 80-120 ℃; the drying time is preferably 8 to 12 hours; the drying temperature is preferably 80-120 ℃; the drying time is preferably 8-12 hours;
and/or the polymer material to be foamed is the same as the polymer matrix in the nucleating agent master batch; the polymer material to be foamed is preferably polyethylene terephthalate;
and/or, the granulation is to add the mixture of the polymer material to be foamed and the nucleating agent master batch into a double-screw extruder for melt blending, then extrude and dry;
wherein the temperature of the working zone of the twin-screw extruder is preferably 180-275 ℃; the working area is preferably divided into five zones, the temperatures being: the first zone is 185-200 ℃, the second zone is 255-265 ℃, the third zone is 260-270 ℃, the fourth zone is 265-275 ℃ and the fifth zone is 265-275 ℃;
wherein the die temperature of the twin-screw extruder is preferably 265 to 275 ℃, for example 270 ℃;
wherein the screw speed of the twin-screw extruder is preferably 240 to 300rpm, for example 280rpm;
and/or the foaming process comprises the steps of sequentially heating, preserving heat, cooling, preserving heat and reducing pressure of the mixture of the granulated foaming raw material and the foaming agent;
wherein the temperature of the temperature rise and the heat preservation is preferably 260-270 ℃, such as 265 ℃;
wherein the pressure for raising and maintaining the temperature is preferably 12-18MPa, such as 15MPa;
wherein the temperature of the temperature reduction and heat preservation is 240-250 ℃, such as 245 ℃;
wherein the reduced pressure is preferably reduced to 0.1MPa;
wherein the rate of depressurization is preferably 200-400MPa/s, such as 300MPa/s;
wherein, the foaming agent is preferably one or more of cyclopentane, supercritical carbon dioxide and supercritical nitrogen.
10. A foamed material, characterized in that it is produced by the process for producing a foamed material according to claim 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211543350.3A CN115772320A (en) | 2022-12-02 | 2022-12-02 | Nucleating agent master batch, foaming material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211543350.3A CN115772320A (en) | 2022-12-02 | 2022-12-02 | Nucleating agent master batch, foaming material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115772320A true CN115772320A (en) | 2023-03-10 |
Family
ID=85391279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211543350.3A Pending CN115772320A (en) | 2022-12-02 | 2022-12-02 | Nucleating agent master batch, foaming material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115772320A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1102844A (en) * | 1965-10-13 | 1968-02-14 | Algemene Kunstzijde Unie Nv | Process for producing injection moulding of articles from a moulding material based on polyesters |
| US20070059511A1 (en) * | 2004-03-31 | 2007-03-15 | Edwards Walter L | Low density foamed polymers |
| JP2014141563A (en) * | 2013-01-23 | 2014-08-07 | Dm Novafoam Ltd | Expandable resin composition and foam |
| CN106046483A (en) * | 2016-06-27 | 2016-10-26 | 湖北祥源新材科技股份有限公司 | Sound absorption and thermal insulation polyolefin foamed sheet and preparation method thereof |
| KR20170080998A (en) * | 2015-12-31 | 2017-07-11 | 주식회사 휴비스 | Masterbatch composition, and preparation method of polyester resin foam using the same |
| CN113025007A (en) * | 2021-03-18 | 2021-06-25 | 浙江恒澜科技有限公司 | Polyester foam material and preparation method thereof |
| CN114106365A (en) * | 2021-11-12 | 2022-03-01 | 南京越升挤出机械有限公司 | Preparation method of polystyrene foaming nucleating agent master batch and foamed polystyrene using nucleating agent master batch |
-
2022
- 2022-12-02 CN CN202211543350.3A patent/CN115772320A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1102844A (en) * | 1965-10-13 | 1968-02-14 | Algemene Kunstzijde Unie Nv | Process for producing injection moulding of articles from a moulding material based on polyesters |
| US20070059511A1 (en) * | 2004-03-31 | 2007-03-15 | Edwards Walter L | Low density foamed polymers |
| JP2014141563A (en) * | 2013-01-23 | 2014-08-07 | Dm Novafoam Ltd | Expandable resin composition and foam |
| KR20170080998A (en) * | 2015-12-31 | 2017-07-11 | 주식회사 휴비스 | Masterbatch composition, and preparation method of polyester resin foam using the same |
| CN106046483A (en) * | 2016-06-27 | 2016-10-26 | 湖北祥源新材科技股份有限公司 | Sound absorption and thermal insulation polyolefin foamed sheet and preparation method thereof |
| CN113025007A (en) * | 2021-03-18 | 2021-06-25 | 浙江恒澜科技有限公司 | Polyester foam material and preparation method thereof |
| CN114106365A (en) * | 2021-11-12 | 2022-03-01 | 南京越升挤出机械有限公司 | Preparation method of polystyrene foaming nucleating agent master batch and foamed polystyrene using nucleating agent master batch |
Non-Patent Citations (1)
| Title |
|---|
| KWON, DONG EUI: "Preparation of polyethylene terephthalate foams at different saturation temperatures using dual methods of supercritical batch foaming", 《KOREAN JOURNAL OF CHEMICAL ENGINEERING》, vol. 38, no. 12, 18 September 2021 (2021-09-18), pages 2560 - 2566, XP037639370, DOI: 10.1007/s11814-021-0889-y * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109605708B (en) | Thermoplastic polyester extrusion foaming forming method | |
| CN102675842B (en) | Polylactic acid foamed material and preparation method thereof | |
| CN101962455B (en) | Injection microcellular foamed wood-plastic composite material and preparation method thereof | |
| CN112679921B (en) | Ionomer composite nucleating agent for PET extrusion foaming and preparation method and application thereof | |
| CN104845300B (en) | A kind of lactic acid composite material for 3 D-printing and preparation method thereof | |
| WO2020083049A1 (en) | Tps/pla/pbat blend modified biodegradable resin prepared by using chain extender and preparation method therefor | |
| CN107177052B (en) | Light polyether-ether-ketone or composite material plate with different crystallinities and preparation method thereof | |
| CN108530752B (en) | Micro-foaming continuous long glass fiber reinforced polypropylene composite material and preparation method and application thereof | |
| CN114989583A (en) | Acid nucleating agent for polyhydroxyalkanoate and polyhydroxyalkanoate molded body | |
| CN111534064B (en) | Polylactic acid with high stereospecific composite content and preparation method thereof | |
| CN112940468A (en) | Polylactic acid-based foaming particles and preparation method thereof | |
| EP4375048A1 (en) | Polyhydroxyalkanoate molded body and preparation method therefor | |
| CN114989586A (en) | Polyhydroxyalkanoate composition containing alcohol nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof | |
| CN110016213B (en) | Polylactic acid foaming material with micro-nano composite pores and preparation method thereof | |
| CN114989581A (en) | Biodegradable polylactic acid foaming particle and preparation method thereof | |
| CN108912380B (en) | Method for preparing high-rate polymer foam by using PMMA/PVDF blend under low-pressure condition | |
| CN115772320A (en) | Nucleating agent master batch, foaming material and preparation method thereof | |
| CN109265825B (en) | Polypropylene or polypropylene compound foamed product and preparation method thereof | |
| CN115322528B (en) | PET foaming core material with high shear strength | |
| CN107474495B (en) | Modified PBAT resin composition and preparation method thereof | |
| CN114685983B (en) | PA56 composition and preparation method and application thereof | |
| CN114773810A (en) | High-performance polylactic acid-based 3D printing wire rod and preparation method thereof | |
| CN114716794A (en) | PBAT foaming bead and preparation method thereof | |
| CN113502041A (en) | Polylactic acid composition containing phosphate nucleating agent and preparation method thereof | |
| CN113845689B (en) | Degradable material foamed by supercritical carbon dioxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |