CN106626640B - A kind of polyester film and preparation method thereof - Google Patents
A kind of polyester film and preparation method thereof Download PDFInfo
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- CN106626640B CN106626640B CN201611176544.9A CN201611176544A CN106626640B CN 106626640 B CN106626640 B CN 106626640B CN 201611176544 A CN201611176544 A CN 201611176544A CN 106626640 B CN106626640 B CN 106626640B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
- B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0264—Polyester
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Manufacturing & Machinery (AREA)
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Abstract
The present invention relates to a kind of polyester films and preparation method thereof, and preparation method includes the following steps：By polycarbodiimide metal complex and polyethylene terephthalate mixing extruding pelletization, resistant to hydrolysis master batch is made；The curtain coating slab that three-layer composite structure is made in slab machine is squeezed out by three-layer co-extruded curtain coating, sandwich layer is made in the mixed resistant to hydrolysis master batch and polyethylene terephthalate, upper layer is made in the mixed resistant to hydrolysis master batch, polyethylene terephthalate and foaming master batch；Thermal finalization is carried out after curtain coating slab is stretched, and polyester film is made；Polycarbodiimide metal complex has the structure as shown in formula III.Polyester film mechanics, the electric property of the present invention is good, and excellent hydrolysis resistance.
Description
Technical field
The present invention relates to the preparation methods of a kind of polyester film and the polyester film.
Background technology
Effectively to prevent the hydrolysis of PET, some additives need to be added to inhibit or control the generation of end carboxyl.It is most commonly seen
Be exactly capping reagent, a portion is also referred to as " anti-hydrolysis agent ".Using various capping reagent/anti-hydrolysis agents in polyester
In resistant to hydrolysis, once by national starch, Baeyer, Rhein chemistry, BASF, joint chemistry, eastern beautiful, Supreme Being people, Du Pont and Rhodia
It reported.In the additive being had been reported that, polycarbodiimide is the most useful one kind.
Polycarbodiimide, usually can be by carrying out removing dioxy as stabilisers against hydrolysis by organic diisocyanate
Change carbon and polymerisation and is made.The organic diisocyanate of two molecules, which can obtain, simplest contains a molecule carbodiimides
Compound, further polymerisation can get containing the polymer that multiple carbodiimide groups and isocyanates are end group,
The degree of polymerization is typically in the range of between 2~30.
Polycarbodiimide is usually to be used as catalyst in organic phosphorus compound, and reaction is obtained under certain temperature, pressure.In
State patent CN201380060155.8 discloses a kind of method preparing polycarbodiimide, wherein selection Phospholes, phosphorus
One or more of heterocyclic pentene oxide, diethoxyphosphinylthiocholine, diethoxyphosphinylthiocholine oxide are as catalysis
Agent, under 20~250 DEG C, the pressure of 20~800mbar, certain nitrogen flow, in HDI, IPDI, TDI, MDI one kind or
It is several that polycarbodiimide is made for monomer reaction.
European patent EP 0808828 discloses in the presence of 5000ppm catalyst, originates in 185 DEG C of polymerizations by TMXDI
The polycarbodiimide that the degree of polymerization is 3.5 is made within 10 hours, but without specifically proposing that inertia protects the use technique and ginseng of gas
Number, only broadly proposes that the reaction can carry out in inert gas shielding.
Chinese patent CN200610082544.2 discloses a kind of preparation method of modified polycarbodiimide composition, especially
It is low to the dissolubility of various solvents for polycarbodiimide, and carbodiimide-based also can slowly occur under solution state
, there is gelation in the reaction of group, the agglutination of polymer, it is difficult to which long-term the problem of storing is solved.It mainly utilizes a certain amount of
Diisopropylamine stirred under room temperature or heating condition with the polycarbodiimide of aromatic diisocyanate compounds, react from
And obtain modified polycarbodiimide.
But for polycarbodiimide in high temperature BOPET production processes, it can usually decompose and generate noxious material isocyanic acid
Ester and isocyanide acid derivative.It is decomposed in plastic processes to reduce polycarbodiimide, it is sub- usually to improve poly- carbonization two
The amine degree of polymerization can greatly improve the thermal stability of anti-hydrolysis agent.Such as 1977, Chemistry In China study on the synthesis used 2,4- bis-
Toluene prepares polymerization carbodiimides.Some synthetic methods have also been developed in Zhejiang University professor Ye Dequan, using 2,4- diformazans
Phenylene diisocyanate prepares 2,2', 6,6'- tetra isopropyl diphenyl carbodiimides by sodium phenolate catalyzing and condensing.
But the activity of the anti-hydrolysis agent of high molecular weight is greatly reduced, and needs to add a greater amount of polycarbodiimide ability
Reach the requirement of hydrolysis-resistant polyester film.Carbodiimides is the dimer of low molecular weight, has very high end capping reaction activity, but
It is easily decomposed at high temperature, the requirement that some plastics are processed under the high temperature conditions is not achieved, therefore do not have high thermal stability.
Invention content
The technical problem to be solved by the present invention is to, provide that a kind of mechanics, electric property are good, and excellent hydrolysis resistance
The preparation method of polyester film and the polyester film.
A kind of technical solution that the present invention proposes to solve above-mentioned technical problem is：A kind of preparation method of polyester film, packet
Include following steps：
A. by the polyethylene terephthalate of the polycarbodiimide metal complex and 3~5 parts by weight of 1 parts by weight
Extruding pelletization is mixed, resistant to hydrolysis master batch is made；Preferable scheme is that：By the polycarbodiimide metal complex of 1 parts by weight and
The polyethylene terephthalate mixing extruding pelletization of 3.5~4.5 parts by weight；Preferred scheme is：By the poly- of 1 parts by weight
The polyethylene terephthalate mixing extruding pelletization of carbodiimides metal complex and 4 parts by weight；
B. the resistant to hydrolysis master batch of 1 parts by weight and the polyethylene terephthalate of 45~55 parts by weight are mixed, preferably
Scheme be：The resistant to hydrolysis master batch of 1 parts by weight and the polyethylene terephthalate of 47~51 parts by weight are mixed, more preferably
Scheme be：The resistant to hydrolysis master batch of 1 parts by weight and the polyethylene terephthalate of 49 parts by weight are mixed,
By the resistant to hydrolysis master batch of 1 parts by weight, the polyethylene terephthalate and 0.8~1.5 weight of 45~55 parts by weight
The foaming master batch mixing of part is measured, Preferable scheme is that：By the resistant to hydrolysis master batch of 1 parts by weight, poly- pair of 46.5~51.5 parts by weight
The foaming master batch of ethylene terephthalate and 0.8~1.5 parts by weight mixes, and preferred scheme is：By the water resistant of 1 parts by weight
Solve the foaming master batch mixing of master batch, the polyethylene terephthalate of 48 parts by weight and 1 parts by weight；
C. the curtain coating slab that three-layer composite structure is made in slab machine is squeezed out by three-layer co-extruded curtain coating, wherein will mix
Sandwich layer is made in the resistant to hydrolysis master batch and polyethylene terephthalate afterwards, by the mixed resistant to hydrolysis master batch, gathers
Layer is made in ethylene glycol terephthalate and foaming master batch；
D. thermal finalization is carried out after the curtain coating slab being stretched, and polyester film is made；
The polycarbodiimide metal complex has the structure as shown in formula III,
Wherein, n is the number containing constitutional repeating unit in copolymer, and n >=2, M are the Ith B races of the periodic table of elements, the IIth B
Transition metal ions in race or the VIIIth race.
Above-mentioned M is Zn2+、Co2+Or Mn2+。
Above-mentioned n >=30.
Above-mentioned n >=50.
In above-mentioned steps B, resistant to hydrolysis master batch is in advance in 100 DEG C~130 DEG C dry 2h~3h.
In above-mentioned steps A, the temperature of extruding pelletization is 260 DEG C~280 DEG C.
In above-mentioned steps B, polyethylene terephthalate crystallizes 4h~6h at 150 DEG C~170 DEG C in advance, then 100
DEG C~130 DEG C of dry 4h~5h；Foaming master batch is in advance in 100 DEG C~130 DEG C dry 2h~3h.
In above-mentioned steps D, the curtain coating slab is first cooled to 35 DEG C hereinafter, elder generation longitudinal stretching, longitudinal stretching when stretching
Temperature be 120 DEG C~140 DEG C, longitudinal stretching multiple is 3.1~3.3 times, then cross directional stretch, and temperature stretching in the transverse direction is 150
DEG C~170 DEG C, longitudinal stretching multiple is 2.9~3.1 times, and when thermal finalization, temperature is 210 DEG C~230 DEG C, the time be 15s~
30s。
The thickness of above-mentioned upper epidermis accounts for the 5%~15% of polyester film overall thickness, preferably 10%；The thickness of the layer accounts for
The 5%~15% of polyester film overall thickness, preferably 10%.
Another technical solution that the present invention proposes to solve above-mentioned technical problem is：It is a kind of using above-mentioned preparation method
Obtained polyester film.
The present invention has the effect of positive：
(1) polyester film of the invention gathers carbonization using special polycarbodiimide metal complex as anti-hydrolysis agent
Diimine metal complex compound, with reacting metal salt solution, forms supermolecule metal complex to contain pyridine carbodiimides as monomer
Object has many advantages, such as that high polymerization degree, high temperature resistant, the addition of metallic framework more improve the hydrolytic Resistance of polymer, resistant to hydrolysis
The intrinsic viscosity of agent is 1.2dL/g~1.5dL/g, and nitrogen atmosphere originates heat decomposition temperature T3%≥280℃.Especially the degree of polymerization exists
50 or more polycarbodiimide metal complex thermal stability higher, compatibility is more preferable, and resistant to hydrolysis is more efficient, can be more
Effectively inhibit the hydrolysis of PET, it is possible to reduce the generation of harmful toxic matter in solar energy backboard membrane production process.
(2) polyester film of the invention has ABA three-layer composite structures, and sandwich layer is by the resistant to hydrolysis master batch of special ratios and poly- pair
Ethylene terephthalate is made, upper layer by special ratios resistant to hydrolysis master batch, polyethylene terephthalate and hair
Bubble master batch is made, and resistant to hydrolysis master batch polycarbodiimide metal complex and polyethylene terephthalate are according to specific ratio
Example mixing extruding pelletization, not only hydrolytic resistance is excellent, and by rationally controlling each component so that polyester film tensile strength,
The electric properties such as the mechanical properties such as percent thermal shrinkage, elongation at break and power frequency electrical strength, shelf depreciation voltage all conform to
It asks, and anti-hydrolytic performance is splendid, and production cost is relatively low.
Description of the drawings
Fig. 1 is the infrared spectrogram of the polycarbodiimide metal complex of the embodiment of the present invention 1.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the polycarbodiimide metal complex of the embodiment of the present invention 1.
Specific implementation mode
Raw materials and reagents used in the embodiment of the present invention are product common in the market, be can be used：
Polyethylene terephthalate (PET), is produced by China Petroleum Liao Yang petrochemical company, inherent viscosity 0.7dl/
g。
Polyester foamed master batch is produced, product type HYDROCEROL by Switzerland's Clariant Corporation (Clariant), and characteristic is viscous
Spend 0.44dl/g.Ingredient of the foaming agent in polyester foamed master batch is 20%, i.e. foaming agent and polyethylene terephthalate
Weight ratio be 1:4.
2,4- diisocyanate pyridines, analysis is pure, is purchased from FCH Group reagents for synthesis；
Di-n-butylamine, tetrahydrofuran, bromjophenol blue, ethyl alcohol, ethylene glycol, dichloromethane, acetone, isopropanol, CoCl2·6H2O,
MnCl2·4H2O, Zn (NO3)2·6H2O, these above-mentioned reagents are that analysis is pure, are purchased from Sinopharm Chemical Reagent Co., Ltd..
3- methyl-1s-phenyl -2- ring fourth phosphorus alkene -1- oxides, analysis is pure, is purchased from the limited public affairs of Shanghai source leaf biotechnology
Department.
Embodiment 1
The preparation method of the polycarbodiimide metal complex of the present embodiment, includes the following steps：
Step 1: under the nitrogen atmosphere protection that nitrogen flow rate is 2L/h, equipped with blender and reflux condenser
It is tested in 1000mL four-hole boiling flasks.2, the 4- diisocyanate pyridines for weighing 0.1mol are put into four-hole boiling flask, will be catalyzed
The 3- methyl-1s of agent 0.5mmol-phenyl -2- ring fourth phosphorus alkene -1- oxides are homogeneously added into 2,4- diisocyanate pyridines, are gathered
140 DEG C of reaction temperature is closed, 4h is reacted.Reaction equation is as follows：
Content by measuring-the NCO of reaction mixture monitors extent of reaction.
In reaction mixture-NCO content can be titrated by di-n-butylamine method and be calculated, program is as follows：
(1) 3.5g~6.5g performed polymers are weighed, dried flask is put into；
(2) 20mL di-n-butylamines solution (in the volumetric flask toluene of the di-n-butylamine drying of 338mL is added with pipette
It is diluted to 1000mL)；
(3) tetrahydrofuran of 50mL dryings is added, stirs evenly；
(4) 100mL anhydrous isopropyl alcohols are added, make indicator with 0.5mL bromjophenol blue ethanol solutions；
(5) it is titrated to yellow terminal with the hydrochloric acid solution of 1.0N；
(6) blank test is done, then the degree of calculating-NCO：
%NCO=(mLHCl blank-mLHCl samples)/example weight × 4.2.
When isocyanate content drops to 5.9wt%, a certain amount of ethylene glycol is added, make in mixture the content of-NCO with-
The content molar ratio of OH is 7:1, end capping reaction 2h is carried out at 80 DEG C controls the stability of product to reduce the activity of end group.
Step 2: the product after sealing end is dissolved in dichloromethane and acetone mixed solvent, CoCl2·6H2O solution returns
100 DEG C of reaction temperature is flowed, flow back 48h.Product after sealing end determines that the degree of polymerization is 71 through molecule measuring test instrument GPC, reaction equation
It is as follows：
After being cooled to room temperature, filtering, ethyl alcohol washs three times, obtains polycarbodiimide metal complex (PCD-Co-71).
Infrared spectrum detection and magnetic resonance detection are carried out respectively to the final product obtained by the present embodiment, obtained infrared light
Spectrogram as shown in Figure 1, obtained nuclear magnetic resonance spectroscopy as shown in Fig. 2, obtained hydrogen nuclear magnetic resonance modal data is as shown in table 2, from
And it is polycarbodiimide metal complex (PCD-Co-71) to verify product.
1 structural characterization spectral data of table
Embodiment 2
The preparation method of the polycarbodiimide metal complex of the present embodiment, includes the following steps：
Step 1: under the nitrogen atmosphere protection that nitrogen flow rate is 2L/h, equipped with blender and reflux condenser
It is tested in 1000mL four-hole boiling flasks.2, the 4- diisocyanate pyridines for weighing 0.1mol are put into four-hole boiling flask, will be catalyzed
The 3- methyl-1s of agent 0.6mmol-phenyl -2- ring fourth phosphorus alkene -1- oxides are homogeneously added into 2,4- diisocyanate pyridines, are gathered
140 DEG C of reaction temperature is closed, 5h is reacted.Content by measuring-the NCO of reaction mixture monitors extent of reaction.
When isocyanate content drops to 2.7wt%, a certain amount of ethylene glycol is added, make in mixture the content of-NCO with-
The content molar ratio of OH is 7 ︰ 1, and end capping reaction 2h is carried out at 80 DEG C and controls the stability of product to reduce the activity of end group.
Step 2: the product after sealing end is dissolved in dichloromethane and acetone mixed solvent, MnCl2·4H2O solution returns
150 DEG C of reaction temperature is flowed, flow back 48h.Product after sealing end determines that the degree of polymerization is 68 through molecule measuring test instrument GPC.It is cooled to
After room temperature, filtering, ethyl alcohol washs three times, obtains polycarbodiimide metal complex (PCD-Mn-68).
Embodiment 3
The preparation method of the polycarbodiimide metal complex of the present embodiment, includes the following steps：
Step 1: under the nitrogen atmosphere protection that nitrogen flow rate is 2L/h, equipped with blender and reflux condenser
It is tested in 1000mL four-hole boiling flasks.2, the 4- diisocyanate pyridines for weighing 0.1mol are put into four-hole boiling flask, will be catalyzed
The 3- methyl-1s of agent 0.4mmol-phenyl -2- ring fourth phosphorus alkene -1- oxides are homogeneously added into 2,4- diisocyanate pyridines, are gathered
150 DEG C of reaction temperature is closed, 4h is reacted.Content by measuring-the NCO of reaction mixture monitors extent of reaction.
When isocyanate content drops to 8.3wt%, a certain amount of ethylene glycol is added, make in mixture the content of-NCO with-
The content molar ratio of OH is 7 ︰ 1, and end capping reaction 2h is carried out at 80 DEG C and controls the stability of product to reduce the activity of end group.
Step 2: the product after sealing end is dissolved in dichloromethane and acetone mixed solvent, Zn (NO3)2·6H2O is molten
Liquid, 150 DEG C of back flow reaction temperature, flow back 48h.Product determines that the degree of polymerization is 50 through molecule measuring test instrument GPC after sealing end.It is cooling
To room temperature, filtering, ethyl alcohol washs three times, obtains polycarbodiimide metal complex (PCD-Zn-50).
The remaining reaction condition of the embodiment of the present invention 3 to embodiment 9 is same as Example 1, and difference is as shown in table 2,
Table 2 is reaction condition table of the embodiment of the present invention 1 to embodiment 9.
2 embodiment reaction condition table of table
The present invention can, reaction time slightly higher by controlling reaction temperature it is longer and control isocyanate content is fewer,
So that the degree of polymerization is higher, the hydrolytic Resistance of product is better.
Application examples 1
The preparation method of the polyester film of the application example, includes the following steps：
A. raw material preparation：
The polycarbodiimide metal complex of 1 parts by weight and the polyethylene terephthalate of 4 parts by weight are mixed
Resistant to hydrolysis master batch is made in extruding pelletization.The temperature of extruding pelletization is 270 DEG C.Resistant to hydrolysis master batch is at 120 DEG C, dry 2h.Gather to benzene
Naphthalate crystallizes 5h at 160 DEG C, then in 120 DEG C of dry 4h by crystallizing and drying machine.Foaming master batch is done at 100 DEG C
Dry 2h.
B. raw material mixes：
By the polyethylene terephthalate of the resistant to hydrolysis master batch and 49 parts by weight of 1 parts by weight, pass through homogenizer
It is mixed.By the foaming of the resistant to hydrolysis master batch of 1 parts by weight, the polyethylene terephthalate and 1 parts by weight of 48 parts by weight
Master batch is mixed by homogenizer, and homogenizer rotating speed is 750r/min.
C. melting extrusion：
Slab machine is squeezed out by three-layer co-extruded curtain coating, by the mixed resistant to hydrolysis master batch and poly terephthalic acid second
Diol ester is extruded into sandwich layer by twin-screw master, by the mixed resistant to hydrolysis master batch, polyethylene terephthalate and
Foaming master batch is extruded into upper layer by the way that twin-screw is auxiliary, to the compound curtain coating slabs of tri- layers of the ABA formed.
D. thermal finalization is stretched：
It after curtain coating slab is cooled to 40 DEG C, is stretched, first longitudinal stretching, the temperature of longitudinal stretching is 130 DEG C, longitudinal
Draw ratio is 3.2 times, then cross directional stretch, and temperature stretching in the transverse direction is 160 DEG C, and longitudinal stretching multiple is 3 times.Then heat is carried out
Sizing, heat setting temperature are 220 DEG C, heat-setting time 20s.The polyester that thickness is 250 μm is made finally by winding process
Film.Upper epidermis and the thickness of layer are 25 μm.
The application example prepares polycarbodiimide metal complex (PCD-Co-71) of the polyester film using embodiment 1.
Application examples 2
The preparation method of the polyester film of the application example, includes the following steps：
A. raw material preparation：
The polyethylene terephthalate of the polycarbodiimide metal complex of 1 parts by weight and 4.5 parts by weight is mixed
Extruding pelletization is closed, resistant to hydrolysis master batch is made.The temperature of extruding pelletization is 260 DEG C.Resistant to hydrolysis master batch is at 120 DEG C, dry 3h.Poly- pair
Ethylene terephthalate crystallizes 4h at 170 DEG C, then in 120 DEG C of dry 4h by crystallizing and drying machine.Foaming master batch is at 120 DEG C
Dry 3h.
B. raw material mixes：
By the polyethylene terephthalate of the resistant to hydrolysis master batch and 47 parts by weight of 1 parts by weight, pass through homogenizer
It is mixed.By the resistant to hydrolysis master batch of 1 parts by weight, the polyethylene terephthalate of 46.5 parts by weight and 1.5 parts by weight
Foaming master batch is mixed by homogenizer, and homogenizer rotating speed is 1000r/min.
C. melting extrusion：
Slab machine is squeezed out by three-layer co-extruded curtain coating, by the mixed resistant to hydrolysis master batch and poly terephthalic acid second
Diol ester is extruded into sandwich layer by twin-screw master, by the mixed resistant to hydrolysis master batch, polyethylene terephthalate and
Foaming master batch is extruded into upper layer by the way that twin-screw is auxiliary, to the compound curtain coating slabs of tri- layers of the ABA formed.
D. thermal finalization is stretched：
It after curtain coating slab is cooled to 40 DEG C, is stretched, first longitudinal stretching, the temperature of longitudinal stretching is 120 DEG C, longitudinal
Draw ratio is 3.3 times, then cross directional stretch, and temperature stretching in the transverse direction is 170 DEG C, and longitudinal stretching multiple is 3.1 times.Then it carries out
Thermal finalization, heat setting temperature are 230 DEG C, heat-setting time 25s.It is 300 μm poly- that thickness, which is made, finally by winding process
Ester film.Upper epidermis and the thickness of layer are 30 μm.
The application example prepares polycarbodiimide metal complex (PCD-Co-71) of the polyester film using embodiment 1.
Application examples 3
The preparation method of the polyester film of the application example, includes the following steps：
A. raw material preparation：
The polyethylene terephthalate of the polycarbodiimide metal complex of 1 parts by weight and 5.5 parts by weight is mixed
Extruding pelletization is closed, resistant to hydrolysis master batch is made.The temperature of extruding pelletization is 280 DEG C.Resistant to hydrolysis master batch is at 130 DEG C, dry 2h.Poly- pair
Ethylene terephthalate crystallizes 5h at 165 DEG C, then in 130 DEG C of dry 5h by crystallizing and drying machine.Foaming master batch is at 105 DEG C
Dry 2.5h.
B. raw material mixes：
By the polyethylene terephthalate of the resistant to hydrolysis master batch and 52 parts by weight of 1 parts by weight, pass through homogenizer
It is mixed.By the resistant to hydrolysis master batch of 1 parts by weight, the polyethylene terephthalate of 51.2 parts by weight and 0.8 parts by weight
Foaming master batch is mixed by homogenizer, and homogenizer rotating speed is 800r/min.
C. melting extrusion：
Slab machine is squeezed out by three-layer co-extruded curtain coating, by the mixed resistant to hydrolysis master batch and poly terephthalic acid second
Diol ester is extruded into sandwich layer by twin-screw master, by the mixed resistant to hydrolysis master batch, polyethylene terephthalate and
Foaming master batch is extruded into upper layer by the way that twin-screw is auxiliary, to the compound curtain coating slabs of tri- layers of the ABA formed.
D. thermal finalization is stretched：
It after curtain coating slab is cooled to 40 DEG C, is stretched, first longitudinal stretching, the temperature of longitudinal stretching is 140 DEG C, longitudinal
Draw ratio is 3.3 times, then cross directional stretch, and temperature stretching in the transverse direction is 160 DEG C, and longitudinal stretching multiple is 3 times.Then heat is carried out
Sizing, heat setting temperature are 225 DEG C, heat-setting time 18s.The polyester that thickness is 250 μm is made finally by winding process
Film.Upper epidermis and the thickness of layer are 20 μm.
The application example prepares polycarbodiimide metal complex (PCD-Co-71) of the polyester film using embodiment 1.
Application examples 4
The preparation method of the polyester film of the application example, rest part is identical as application examples 1, the difference is that：
The application example prepares polycarbodiimide metal complex (PCD-Mn-68) of the polyester film using embodiment 2.
Application examples 5
The preparation method of the polyester film of the application example, rest part is identical as application examples 1, the difference is that：
The application example prepares polycarbodiimide metal complex (PCD-Zn-50) of the polyester film using embodiment 3.
Comparative example 1
The preparation method of the polyester film of this comparative example, rest part is identical as application examples 1, the difference is that：
The foaming of the resistant to hydrolysis master batch of 1 parts by weight, the polyethylene terephthalate of 46 parts by weight and 3 parts by weight is female
Grain is mixed and made into layer.
Comparative example 2
The preparation method of the polyester film of this comparative example, rest part is identical as application examples 1, the difference is that：
By the resistant to hydrolysis master batch of 1 parts by weight, the hair of the polyethylene terephthalate and 0.5 parts by weight of 48.5 parts by weight
Bubble master batch is mixed and made into layer.
The polyester film made by application examples 1 to 5 and comparative example 1 and 2 to the present invention is made standard batten and carries out mechanics, water
Vapour transmitance, hydrothermal aging performance test.Detection method used is as shown in table 3.
The detection method table of comparisons of 3 polyester film of table
Testing result is as shown in table 4.
The performance indicator of 4 polyester film of table
As can be known from the above table, the polyester film of application examples 1 to 5 is had excellent performance.And excessive polyester foamed master batch is added, surface layer
Stomata quantity can be more, and the water vapor transmittance of polyester film is substantially reduced, and tensile strength also can be relatively low, final PCT (121 DEG C,
2atm) the anti-hydrolytic performance deviation of 48 hours aging rear films.As shown in comparative example 1, PCT (121 DEG C, 2atm) 48 hours it
Afterwards, the elongation at break of film only has 20%, undesirable.And excessive resistant to hydrolysis master batch is added, the insulating properties of polyester film
Can, as shown in comparative example 2, power frequency electrical strength and local discharge voltage are substantially reduced, while will also result in resistant to hydrolysis polyester film
Finished product go up.
Obviously, the above embodiment is merely an example for clearly illustrating the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the art, it can also be made on the basis of the above description
Its various forms of variation or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
The obvious changes or variations that bright spirit is extended out are still in the protection scope of this invention.
Claims (8)
1. a kind of preparation method of polyester film, which is characterized in that include the following steps：
A. the polycarbodiimide metal complex of 1 parts by weight and the polyethylene terephthalate of 3~5 parts by weight are mixed
Resistant to hydrolysis master batch is made in extruding pelletization；
B. the resistant to hydrolysis master batch of 1 parts by weight and the polyethylene terephthalate of 45~55 parts by weight are mixed, by 1 weight
The foaming master batch of the resistant to hydrolysis master batch of part, the polyethylene terephthalate of 45~55 parts by weight and 0.8~1.5 parts by weight is mixed
It closes；
C. the curtain coating slab that three-layer composite structure is made in slab machine is squeezed out by three-layer co-extruded curtain coating, wherein will be mixed
Sandwich layer is made in the resistant to hydrolysis master batch and polyethylene terephthalate, by the mixed resistant to hydrolysis master batch, gathers to benzene
Layer is made in naphthalate and foaming master batch；
D. thermal finalization is carried out after the curtain coating slab being stretched, and polyester film is made；
The polycarbodiimide metal complex has the structure as shown in formula III,
,
Wherein, n is the number containing constitutional repeating unit in copolymer, n >=50, M Zn2+、Co2+Or Mn2+；
The weight accounting 20% of foaming agent in the foaming master batch.
2. a kind of preparation method of polyester film according to claim 1, which is characterized in that the polycarbodiimide metal
The synthesis step of complex compound is：
Step 1: under nitrogen protection, after 2,4- diisocyanate pyridine shown in suitable formula I reaches polymeric reaction temperature,
Suitable catalyst is added, polymerisation is carried out, when the content of isocyanates is less than 15wt%, suitable ethylene glycol is added, into
Row end capping reaction,
；
Step 2: the product after being blocked shown in formula II is dissolved in solvent, metal salt solution is then added, flow back anti-
It answers, obtains polycarbodiimide metal complex shown in formula III,
；
The metal salt solution is cobalt chloride hexahydrate, four chloride hydrate manganese or zinc nitrate hexahydrate, and the catalyst is 3- first
Base -1- phenyl -2- ring fourth phosphorus alkene -1- oxides；
Polymeric reaction temperature in the step 1 is 60 DEG C~300 DEG C, and the time of polymerisation is 1h~5h, end capping reaction
Temperature is 80 DEG C, and the end capping reaction time is 1h~3h, and the mole that catalyst is added accounts for 2,4- diisocyanate pyridines and rubs
The 0.1%~1% of that amount；
Back flow reaction temperature in the step 2 is 80 DEG C~200 DEG C, and reflux time is 20h or more, the addition gold
The ratio of the mole and the mole of the product after sealing end shown in formula II that belong to salting liquid is 1 ︰ 1, the addition of the ethylene glycol
Amount so that the content molar ratio of content and the-OH of-NCO in the mixture of step 1 is 7 ︰ 1, the solvent be dichloromethane and
The mixed liquor of acetone, after the product of the step 2 is cooled to room temperature, filtering, three times through ethyl alcohol washing.
3. a kind of preparation method of polyester film according to claim 1 or 2, it is characterised in that：In the step B, water resistant
Master batch is solved in advance in 100 DEG C~130 DEG C dry 2h~3h.
4. a kind of preparation method of polyester film according to claim 1 or 2, it is characterised in that：In the step A, squeeze out
The temperature of granulation is 260 DEG C~280 DEG C.
5. a kind of preparation method of polyester film according to claim 1 or 2, it is characterised in that：In the step B, poly- pair
Ethylene terephthalate crystallizes 4h~6h at 150 DEG C~170 DEG C in advance, then in 100 DEG C~130 DEG C dry 4h~5h；Foaming
Master batch is in advance in 100 DEG C~130 DEG C dry 2h~3h.
6. a kind of preparation method of polyester film according to claim 1 or 2, it is characterised in that：In the step D, first will
The curtain coating slab is cooled to 35 DEG C hereinafter, elder generation longitudinal stretching when stretching, the temperature of longitudinal stretching is 120 DEG C~140 DEG C, longitudinal
Draw ratio is 3.1~3.3 times, then cross directional stretch, and temperature stretching in the transverse direction is 150 DEG C~170 DEG C, and longitudinal stretching multiple is
2.9~3.1 times, when thermal finalization, temperature is 210 DEG C~230 DEG C, and the time is 15s~30s.
7. a kind of preparation method of polyester film according to claim 1 or 2, it is characterised in that：The thickness of the upper epidermis
The 5%~15% of polyester film overall thickness is accounted for, the thickness of the layer accounts for the 5%~15% of polyester film overall thickness.
8. a kind of polyester film using obtained by preparation method as described in claim 1.
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