CN1121448C - Polyethylene terephthalate (PET) pipe material and its preparation method - Google Patents
Polyethylene terephthalate (PET) pipe material and its preparation method Download PDFInfo
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- CN1121448C CN1121448C CN 00100843 CN00100843A CN1121448C CN 1121448 C CN1121448 C CN 1121448C CN 00100843 CN00100843 CN 00100843 CN 00100843 A CN00100843 A CN 00100843A CN 1121448 C CN1121448 C CN 1121448C
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Abstract
The present invention relates to a polyethylene terephthalate pipe and a preparation method thereof. The pipe is prepared by polyethylene terephthalate, ethylene copolymer with active groups, and the composition of nucleating agents and grafting agents, and is melted and extruded at 220 to 270 DEGC. The outer diameter of the pipe is 8 to 90mm, the wall thickness is 0.1 to 3mm, and the burst strength is 3 to 14MPa. The pipe is suitable for agriculture water saving irrigation systems and other fluid delivery systems.
Description
The present invention relates to a kind of polyester tubing, specially refer to the tubing and the machining manufacture that adopt the polyethylene terephthalate preparation of compositions.
PET is a kind of polymkeric substance of high comprehensive performance, has high strength, high rigidity, solvent resistance and thermotolerance.PET is as the engineering plastics of excellent performance, is mainly used in the accurate connector of the various parts of automobile, household electrical appliances, business automation equipment and electric and computer.But because its crystallization velocity is slow, melt viscosity is low under high shear forces, has limited its rapid shaping and Application Areas.
Plastic conduit is compared with metal, concrete duct, has advantages such as conveying energy consumption is low, good corrosion resistance, inner wall smooth, so development in recent years is quite rapid, range of application is more and more wider.Because PET has high-modulus, high strength, the pipeline of making of its can replace the pipeline of metal and other material in the larger context, has broad application prospects.
Adopt general PET resin to carry out tubing and extrude,, can not obtain ideal PET tubing usually because the crystallization velocity of melt intensity slow and melt is low.Japan's special permission discloses and discloses a kind of PET composition and tubing thereof among the clear 62-290750, and its composition is made up of PET, nucleator, nucleation accelerating agent and releasing agent.Described composition only can be made the little tubing that external diameter is 6mm, the example of while and unexposed low intrinsic viscosity PET composition.Japan's special permission discloses the preparation method who discloses a kind of PET tubing among the clear 55-32641, and the tubing caliber that this method for making is made is 23mm, and preparation technology requires complexity.
The objective of the invention is to overcome existing in the shortcoming of the single and complicated process of preparation of PET tubing specification, and provide tubing that ethylene copolymer, nucleator, the chain extender composition of a kind of PET of employing, band active group make and preparation method thereof.
PET tubing of the present invention, its raw material are the PET compositions, and said composition comprises following component and content (weight part):
PET?70～99，
The ethylene copolymer 0～30 of band active group,
Nucleator 0.05～5,
Chainextender 0.05～3,
Auxiliary agent 0.02～3.
Above-mentioned polyethylene terephthalate is produced by existing various commercial runs, and its intrinsic viscosity is 0.60～1.20dL/g.It is homopolymerization polyester or copolyester and both mixtures thereof, and its ratio of mixture is 7: 3～3: 7.Described homopolymerization polyester is meant the polymkeric substance that terephthalic acid and ethylene glycol adopt the production of direct esterification method or terephthaldehyde's ester and ethylene glycol to adopt ester-interchange method to produce; Described copolyester is meant multipolymer or terephthalic acid and ethylene glycol and 1 of terephthalic acid and m-phthalic acid and ethylene glycol, the multipolymer of 4-methylol hexanaphthene.
The ethylene copolymer of above-mentioned band active group can be the product of the monomer copolymerization of ethene and band active group, and this comonomer comprises vinylformic acid, methacrylic acid etc.; Also can be ethene with not with the monomer copolymerization of active group, multipolymer again with the ethylene copolymer of the monomer-grafted formation band active group of band active group.This comonomer comprises propylene-1, butene-1, hexene-1, octene-1,4-methylpentene-1, vinyl acetate etc., the grafted reactive monomer has vinylformic acid, n-butyl acrylate, maleic anhydride, fumaric acid, fumaric acid anhydride, methylene-succinic acid, citraconic acid, propylene oxide oxypropyl trimethyl silane, methacrylic acid epoxy glyceride, 2-pseudoallyl-2-oxazoline, as ethene-1-octene copolymer graft glycidyl methacrylate or ethene-n-butyl acrylate copolymer grafted glycidyl methacrylate.The active group of the ethylene copolymer of band active group also comprises carboxylate group in the present composition, it is normally with the ionization product of the ethylene copolymer of carboxylic acid group or anhydride group, ion has sodium ion, potassium ion, zine ion, as the sodium salt of terpolymer EP rubber graft acrylic acid or the sylvite of ethylene-acrylic acid copolymer.。
The ethylene copolymer of the band active group that the present composition adopts can be that a kind of multipolymer that satisfies above-mentioned requirements uses separately, also can be several multipolymers and usefulness.
Above-mentioned nucleator is meant the nucleation interfacial free energy that reduces PET in the PET melt cools, the material that promotes the effect of PET crystallization nucleation, as metal oxide, clay class, inorganic salts and organic acid alkaline metal salt.Metal oxide has titanium dioxide, zinc oxide, magnesium oxide, aluminium sesquioxide etc., the clay class has mica, polynite, talcum powder etc., inorganic salts has barium sulfate, magnesiumcarbonate, calcium phosphate etc., and the organic acid alkaline metal salt has Sodium Benzoate, sodium benzoate, calcium stearate etc.The nucleator that the present invention adopts can be one or more nucleators and the usefulness that meets above-mentioned requirements.
Above-mentioned chainextender is meant the compound that the melt viscosity that can make PET and melt strength increase, it is normally with the compound of two or more functional groups, these functional groups comprise epoxide group, oxazoline group, isocyanate groups etc., as N, N-diepoxy propyl benzamide, 1,3-penylene-two (2-oxazoline), toluene-2,4-diisocyanate, N, N, N ', N '-tetra glycidyl ester-4,4 '-diaminodiphenylmethane etc.
Above-mentioned auxiliary agent comprises various auxiliary agents such as stablizer, flow ability modifying agent, tinting material, dispersion agent.For example, four [β-(3 of Switzerland's Ciba, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Irganox 1010), 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid (Irganox 1222), 2-(2H-benzotriazole-2-yl)-4, thermo-stabilizer and photostabilizers such as 6-di-tert-pentyl phenol (Tinuvin 328) and triphenyl, trimethyl phosphate.These stablizers can independent or compound use, and the addition in composition is 0.01～1% of a weight resin; Preferable consumption is 0.01～0.5% of a weight resin.Tinting material can add with the form of toner or Masterbatch, decides no particular requirement according to required color and hiding rare.Dispersion agent is mainly used in the dispersion of toner or Masterbatch, can be polyethylene wax, chlorinatedpolyethylene wax, Poly Propylene Wax etc., and the consumption of its consumption and tinting material is suitable.
The preparation method who the invention provides a kind of polyethylene terephthalate tubing step in the following order carries out: (1): mix by weight ethylene copolymer 0～30, nucleator 0.05～5, chainextender 0.05～5 and the suitable adjuvants of polyethylene terephthalate 70～99, band active group are put into pre-mixing equipment, form mixture; (2): mixture is added melt mixing equipment (single screw extrusion machine, twin screw extruder, double roll mill etc.) make the material melting mixing even, obtain composition at 270～290 ℃; (3): it is that 8～90mm, wall thickness are the tubing of 0.1～3mm that this composition is made diameter at 225～270 ℃ through extrusion molding machine head, and the extruded velocity of tubing is 1.5～16m/min.This tubing has high bursting strength and high applying pressure, is applicable to agricultural water-saving irrigation system and other fluid delivery systems.
The present invention adopts the more amount polyethylene terephthalate, more on a small quantity with ethylene copolymer, nucleator, the chainextender of active group with comprise stablizer, tinting material, the tubing that dispersion agent is made, have isostatic rigidity and shock resistance, good anti ageing property and long work-ing life, tubing is 3～14MPa at 23 ℃ burstpressures (4.4 carry out in according to standard GB 6674～86).This tubing can satisfy the various requirement that the water saving irrigation system is used tubing.
Content of the present invention can be passed through the further additional explanation of the following example, but can not think that the present invention only only limits to these embodiment.
Embodiment 1
With the intrinsic viscosity that accurately takes by weighing is PET 18Kg, ethene-1-octene copolymer graft glycidyl methacrylate 6.25Kg and the titanium dioxide (TiO of 0.63dL/g
2) 0.125Kg, Sodium Benzoate 0.125Kg, N, N-diepoxy propyl benzamide 0.375Kg, Irganox 1010 0.05Kg, Irganox 1222 0.05Kg, polyethylene wax 0.025Kg place homogenizer to mix.Compound melt extrudes in twin screw extruder, cooling, granulation, and barrel zone temperature is 225～280 ℃, and head temperature is 260 ℃.Gained PET composition is extruded at the enterprising line pipe material of single screw rod pipe extruder group after 24 hours 110 ℃ of vacuum-dryings, the barrel zone temperature of single screw extrusion machine is 225～290 ℃, the temperature of head is 240 ℃, adopt vacuum sizing, the outer diameter of gained tubing is 12mm, wall thickness is 0.5mm, and extruded velocity is 16m/min.Tubing is 3MPa at 23 ℃ burstpressures (4.4 carry out in according to standard GB 6674-86).
Embodiment 2
With the intrinsic viscosity that accurately takes by weighing is that the PET 21.5Kg of 0.94dL/g, sodium salt 2.1Kg and polynite 1.0Kg, toluene-2,4-diisocyanate 0.275Kg, Irganox 1010 0.05Kg, Irganox 1222 0.05Kg, the polyethylene wax 0.025Kg of terpolymer EP rubber graft acrylic acid place homogenizer to mix.Compound melt extrudes in twin screw extruder, cooling, granulation, and barrel zone temperature is 225～280 ℃, and head temperature is 260 ℃.Gained PET composition is extruded at the enterprising line pipe material of single screw rod pipe extruder group after 24 hours 110 ℃ of vacuum-dryings, the barrel zone temperature of single screw extrusion machine is 225～270 ℃, the temperature of head is 258 ℃, adopt vacuum sizing, the outer diameter of gained tubing is 50mm, wall thickness is 2mm, and extruded velocity is 3m/min.Tubing is 10MPa at 23 ℃ burstpressures (4.4 carry out in according to standard GB 6674-86).
Embodiment 3
With the intrinsic viscosity that accurately takes by weighing is the PET 7Kg of 0.74dL/g, terephthalic acid and ethylene glycol and 1 that intrinsic viscosity is 0.73dL/g, and the copolyester 16.3Kg of 4-methylol hexanaphthene, the sylvite 1.2Kg of ethylene-acrylic acid copolymer and polynite 0.1Kg, toluene-2,4-diisocyanate 0.275Kg, Irganox 1010 0.05Kg, Irganox1222 0.05Kg, polyethylene wax 0.025Kg place homogenizer to mix.Compound melt extrudes in twin screw extruder, cooling, granulation, and barrel zone temperature is 225～280 ℃, and head temperature is 260 ℃.Gained PET composition is extruded at the enterprising line pipe material of single screw rod pipe extruder group after 24 hours 110 ℃ of vacuum-dryings, the barrel zone temperature of single screw extrusion machine is 225～270 ℃, the temperature of head is 248 ℃, adopt vacuum sizing, the outer diameter of gained tubing is 25mm, wall thickness is 1mm, and extruded velocity is 5m/min.Tubing is 6MPa at 23 ℃ burstpressures (4.4 carry out in according to standard GB 6674-86).
Embodiment 4
With the intrinsic viscosity that accurately takes by weighing is terephthalic acid and ethylene glycol and 1 of 0.73dL/g, the copolyester 7.35Kg of 4-methylol hexanaphthene, intrinsic viscosity are PET 17.15Kg and barium sulfate 0.2Kg, the N of 1.02dL/g, N, N ', N '-tetra glycidyl ester-4,4 '-diaminodiphenylmethane 0.2Kg, Irganox 1010 0.05Kg, Irganox1222 0.05Kg place homogenizer to mix.Compound is direct extruding pipe material on single screw rod pipe extruder group, and barrel zone temperature is 225～270 ℃, and head temperature is 250 ℃, adopts vacuum sizing, and gained outer pipe wall diameter is 73mm, and wall thickness is 2.5mm, and extruded velocity is 2.5m/min.Tubing is 12MPa at 23 ℃ burstpressures (4.4 carry out in according to standard GB 6674-86).
Embodiment 5
With the intrinsic viscosity that accurately takes by weighing is the terephthalic acid of 0.85dL/g and copolyester 46Kg, the ethene-n-butyl acrylate copolymer grafted glycidyl methacrylate 3Kg and the titanium dioxide (TiO of m-phthalic acid and ethylene glycol
2) 0.1Kg, Sodium Benzoate 0.1Kg, 1,3-penylene-two (2-oxazoline) 0.6Kg, Irganox 10100.1Kg, Irganox 1222 0.1Kg place homogenizer to mix.Compound is direct extruding pipe material on single screw rod pipe extruder group, and barrel zone temperature is 210～270 ℃, and head temperature is 253 ℃, adopts vacuum sizing, and gained outer pipe wall diameter is 90mm, and wall thickness is 3mm, and extruded velocity is 1.5m/min.Tubing is 14MPa at 23 ℃ burstpressures (4.4 carry out in according to standard GB 6674-86).
Claims (8)
1, a kind of polyethylene terephthalate tubing is characterized in that described raw material is the polyethylene terephthalate composition, and said composition comprises following component and content (weight part):
Polyethylene terephthalate 70～99,
The ethylene copolymer 0～30 of band active group,
Nucleator 0.05～5,
Chainextender 0.05～3,
Auxiliary agent 0.02～3,
The intrinsic viscosity of above-mentioned polyethylene terephthalate is 0.60～1.20dL/g,
Above-mentioned nucleator is titanium dioxide, polynite, barium sulfate or Sodium Benzoate,
Above-mentioned chainextender is N, N-diepoxy propyl benzamide, 1,3-penylene-two (2-oxazoline), toluene-2,4-diisocyanate or N, N, N ', N '-tetra glycidyl ester-4,4 '-diaminodiphenylmethane.
2, a kind of polyethylene terephthalate tubing according to claim 1 is characterized in that described polyethylene terephthalate is homopolymerization polyester, copolyester or both with 3: 7～7: 3 mixture.
3, a kind of polyethylene terephthalate tubing according to claim 2 is characterized in that described copolyester is the multipolymer of terephthalic acid and m-phthalic acid and ethylene glycol.
4, a kind of polyethylene terephthalate tubing according to claim 2 is characterized in that described copolyester is terephthalic acid and ethylene glycol and 1, the multipolymer of 4-methylol hexanaphthene.
5, a kind of polyethylene terephthalate tubing according to claim 1, the ethylene copolymer that it is characterized in that described band active group are ethene-1-octene copolymer graft glycidyl methacrylate or ethene-n-butyl acrylate copolymer grafted glycidyl methacrylate.
6, a kind of polyethylene terephthalate tubing according to claim 1, the ethylene copolymer that it is characterized in that described band active group is the sodium salt of terpolymer EP rubber graft acrylic acid or the sylvite of ethylene-acrylic acid copolymer.
7, the preparation method of a kind of polyethylene terephthalate tubing according to claim 1 is characterized in that step is carried out in the following order:
(1): by weight ethylene copolymer 0～30, nucleator 0.05～5, chainextender 0.05～3 and the auxiliary agent 0.02～3 of polyethylene terephthalate 70～99, band active group are put into pre-mixing equipment and mix, form mixture;
(2): the mixture that forms is put into forcing machine, make the material melting mixing even at 270～290 ℃;
(3): the uniform material of melting mixing through former extrude at 225～270 ℃, vacuum cooling typing.
8, the preparation method of a kind of polyethylene terephthalate tubing according to claim 1 is characterized in that described tubing is that diameter is that 8～90mm, wall thickness are the tubing of 0.1～3mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00100843 CN1121448C (en) | 2000-02-17 | 2000-02-17 | Polyethylene terephthalate (PET) pipe material and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00100843 CN1121448C (en) | 2000-02-17 | 2000-02-17 | Polyethylene terephthalate (PET) pipe material and its preparation method |
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| Publication Number | Publication Date |
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| CN1263128A CN1263128A (en) | 2000-08-16 |
| CN1121448C true CN1121448C (en) | 2003-09-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 00100843 Expired - Fee Related CN1121448C (en) | 2000-02-17 | 2000-02-17 | Polyethylene terephthalate (PET) pipe material and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101724230B (en) * | 2008-10-30 | 2011-12-28 | 中国石油化工股份有限公司 | Polyester composition for preparing pipes and preparation method and application thereof |
| CN103030938A (en) * | 2012-12-28 | 2013-04-10 | 江苏百安居管业有限公司 | PET drainage pipe fitting and manufacturing method thereof |
| CN106084676A (en) * | 2016-06-15 | 2016-11-09 | 潘海云 | A kind of PET tubing and preparation technology thereof |
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