CN105504253A - Siloxane-polyester copolymer resin, siloxane-polyester copolymer compound substrate membrane, and methods for preparing siloxane-polyester copolymer resin and siloxane-polyester copolymer compound substrate membrane - Google Patents
Siloxane-polyester copolymer resin, siloxane-polyester copolymer compound substrate membrane, and methods for preparing siloxane-polyester copolymer resin and siloxane-polyester copolymer compound substrate membrane Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
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- 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
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- B32B2250/02—2 layers
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- B32B2307/73—Hydrophobic
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Abstract
The invention discloses siloxane-polyester copolymer resin, a siloxane-polyester copolymer compound substrate membrane, and methods for preparing the siloxane-polyester copolymer resin and the siloxane-polyester copolymer compound substrate membrane. The molecular weight of the siloxane-polyester copolymer resin is 10000-25000. The siloxane-polyester copolymer resin is prepared through reaction between terephthalic acid and a compound containing dyhydroxy. The siloxane-polyester copolymer resin and PET resin are molten through an extruder based on the mass ratio of (10-200) : 100, and then delamination coextrusion with a resin melting distributor, casting strip combination, longitudinal drawing, horizontal drawing, heat setting, cooling and coiling are conducted to obtain the siloxane-polyester copolymer compound substrate membrane. The thickness of the compound substrate membrane prepared from the siloxane-polyester copolymer is 100-300 microns, and the compound substrate membrane is especially suitable for manufacturing of release films and hydrolysis resistance materials for solar photovoltaic cell backboards and is high in performance and practicality.
Description
Technical field
The invention belongs to the preparation of copolymer resin based on polyester and sandwich-like product thereof, relate to a kind of Silicone-Polyester copolymer resin, Silicone-Polyester multipolymer compound substrate membranes and preparation method thereof.Silicone-Polyester copolymer resin of the present invention, Silicone-Polyester multipolymer compound substrate membranes are specially adapted to the manufacture of the material such as hydrolysis of release film, solar photovoltaic cell backplane.
Background technology
As everyone knows, PET (being the abbreviation of polyethylene terephthalate) Biaxially oriented polyester film has excellent mechanical property, chemical property and optical property, but molecular chain exists a large amount of ester bonds to be easily hydrolyzed, film characteristics viscosity is reduced, cause thin film mechanical performance to decline to a great extent, film reduces work-ing life greatly.Therefore, study with polyester is main body silicone-containing-polyethylene terephthalate copolymer ester resin surface performance just seems extremely important.
In prior art, five aspects are mainly concentrated on to the research that the anti-hydrolytic performance of the solar cell backboard basement membrane taking PET polyester (that is: polyethylene terephthalate) resin as material of main part improves: one is, silicone oil or fluorine containing silicone oil off-line coating PET film is adopted to reduce film surface tension force, reach hydrophobic object, thus improve film anti-hydrolytic performance, but this mode generally adopts solvent method, production process electrostatic easily causes solvent inflammable and explosive; Two are, the open CN101899198A of Chinese patent adds the anti-hydrolytic performance improving PET film based on the hydrolysis stabilizer of epoxidised fatty acid ester and a certain amount of epoxidised glycerin fatty acid ester in the film, hydrolysis stabilizer due to epoxidised fatty acid ester has a small amount of gel and produces in film production, can affect film appearance on the one hand; Gel can produce stress concentration, the easy rupture of membranes of film-forming process on the other hand; Three are, Japanese Patent JP2002-026354 improves PET film hydrolytic resistance by using high molecular PET resin, this mode improves to raising PET film anti-hydrolytic performance, but in film manufacturing processes, because PET molecular weight is high, film stretching difficulty, cross directional stretch is de-folder easily, and film rupture of membranes rate is large; Four are, Japanese Patent JP2009-045888: adopt the blended hydrolytic resistance improving PET film of PEN and PET, PET/PEN co-mixing system PEN content is 20% ~ 80%, system is non-crystallizable, affect thin film physics mechanical property, Film shrinkage is comparatively large, if PEN content is lower than 20%, does not then substantially improve the anti-hydrolytic performance of PET; If PEN content is higher than 80%, then masking difficulty, with existing PET film drawing device, is difficult to realize membrane.
Summary of the invention
Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, provides a kind of Silicone-Polyester copolymer resin, Silicone-Polyester multipolymer compound substrate membranes and preparation method thereof.The present invention adopts in PET resin in-situ polymerization, hydroxy-end capped for hydrophobicity fluorosilicon oil (containing dimethylsiloxane compounds) is received in the conjugated polyester resin molecular backbone chain based on PET segment, to reach the object of its multipolymer, compound substrate membranes hydrolysis.
Content of the present invention is: a kind of Silicone-Polyester copolymer resin, is characterized in that: the general formula of molecular structure of described Silicone-Polyester copolymer resin is:
In formula:
or
wherein: m is 25 ~ 40, n be 10 ~ 20, X be 5 ~ 10, Y is 3 ~ 5, m, n, X and Y are integer;
The limiting viscosity of described Silicone-Polyester copolymer resin is 0.60dl/g ~ 0.68dl/g, and melting range is 240 DEG C ~ 253 DEG C, and molecular weight is 10000 ~ 25000;
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1050mol ~ 1200mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 230 DEG C ~ 250 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start (slowly) pressure release, add (catalyzer) 0.13mol ~ 0.23mol antimonous oxide, (stablizer) 0.025mol ~ 0.036mol triphenylphosphate, stir 15min ~ 20min, then starting (slowly) vacuumizes, to reactor, overbottom pressure is less than 60Pa, and be warming up to 280 DEG C ~ 290 DEG C and carry out polycondensation, polycondensation time 3h ~ 4h, be filled with N
2(nitrogen) discharging, i.e. obtained Silicone-Polyester copolymer resin,
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=800 ~ 950:100 ~ 400 ethylene glycol with contain dimethylsiloxane compounds and mix and form;
Described is one or both mixture in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane) containing dimethylsiloxane compounds.
Another content of the present invention is: a kind of Silicone-Polyester multipolymer compound substrate membranes, it is characterized in that: described Silicone-Polyester multipolymer compound substrate membranes is made up of the Silicone-Polyester copolymer film (being called for short: A layer) of A layer and PET film (being called for short: the B layer) compound of B layer, its laminate structure is that A/B is two-layer, thickness is 100 μm ~ 300 μm, the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 10 ~ 200:100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h, at 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is 0.8g/m
224h ~ 1.2g/m
224h,
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 10 ~ 200 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 15 DEG C ~ 25 DEG C, again through 2.8 ~ 3.3 times of longitudinal stretchings, 2.9 ~ 3.4 times of cross directional stretchs, heat setting type at temperature 190 DEG C ~ 230 DEG C, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Another content of the present invention is: a kind of Silicone-Polyester multipolymer compound substrate membranes, it is characterized in that: described Silicone-Polyester multipolymer compound substrate membranes is made up of the PET film (be called for short: B layer) of B layer and the Silicone-Polyester copolymer film (abbreviation: A layer) of A layer on the PET film two sides that is compounded in B layer, its laminate structure is A/B/A tri-layers two kinds, thickness is 100 μm ~ 300 μm, the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 10 ~ 200:100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h, at 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is 0.8g/m
224h ~ 1.2g/m
224h,
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 10 ~ 200 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 15 DEG C ~ 25 DEG C, again through 2.8 ~ 3.3 times of longitudinal stretchings, 2.9 ~ 3.4 times of cross directional stretchs, heat setting type at temperature 190 DEG C ~ 230 DEG C and obtaining,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Another content of the present invention is: a kind of preparation method of Silicone-Polyester multipolymer compound substrate membranes, it is characterized in that step is:
A, prepare silicone-containing-polyethylene terephthalate copolymer resin:
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1050mol ~ 1200mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 230 DEG C ~ 250 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start (slowly) pressure release, add (catalyzer) 0.13mol ~ 0.23mol antimonous oxide, (stablizer) 0.025mol ~ 0.036mol triphenylphosphate, stir 15min ~ 20min, then starting (slowly) vacuumizes, to reactor, overbottom pressure is less than 60Pa, and be warming up to 280 DEG C ~ 290 DEG C and carry out polycondensation, polycondensation time 3h ~ 4h, be filled with N
2(nitrogen) discharging, namely obtained Silicone-Polyester copolymer resin, for subsequent use,
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=800 ~ 950:100 ~ 400 ethylene glycol with contain dimethylsiloxane compounds and mix and form;
Described one or both the mixture referred to containing dimethylsiloxane compounds in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane);
B, prepare Silicone-Polyester multipolymer compound substrate membranes:
The Silicone-Polyester copolymer resin prepared by step a and PET resin are that 10 ~ 200:100 gets the raw materials ready respectively in mass ratio, and respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, compound slab on cold drum at temperature 15 DEG C ~ 25 DEG C, compound slab again at temperature 70 C ~ 80 DEG C through 2.7 ~ 3.3 times of longitudinal stretchings, then temperature 45 C ~ 60 DEG C are cooled to through 1s ~ 5s, 2.8 ~ 3.4 times of cross directional stretchs are carried out again at temperature 110 DEG C ~ 130 DEG C, film through two-way stretch enters electrically heated passage heat set zone, wherein first district's temperature is 200 DEG C ~ 210 DEG C, secondth district is 210 DEG C ~ 215 DEG C, 3rd district is 215 DEG C ~ 220 DEG C, 4th district is 215 DEG C ~ 220 DEG C, 5th district is 225 DEG C ~ 230 DEG C, 6th district is 190 DEG C ~ 200 DEG C, film thermal shaping time is 8s ~ 120s, the cooling in two stages under temperature 60 C ~ 70 DEG C, time 6s ~ 20s and room temperature again of film through heat set zone, rolling, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
The thickness of described obtained Silicone-Polyester multipolymer compound substrate membranes is 100 μm ~ 300 μm, and anti-hydrolytic performance is: when 121 DEG C of boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH test environment, water vapor transmission rate (WVTR) 0.8g/m
224h ~ 1.2g/m
224h.
The Silicone-Polyester multipolymer compound substrate membranes that step b obtains can be A/B two laminate or A/B/A tri-laminate.
Compared with prior art, the present invention has features and beneficial effect:
(1) structure of Silicone-Polyester multipolymer compound substrate membranes material of the present invention adopts the two-layer or A/B/A three-decker of A/B, and namely one deck is the hydrolysis layer with hydrophobic function; Another layer is the pet layer with general conventional func; The hydrolysis layer of hydrophobic function adopts in PET in-situ polymerization, a part is had hydrophobic function and adopt in-situ polymerization mode containing dimethylsiloxane compounds, repeating unit with hydrophobic grouping is received on PET molecular chain, thus make have hydrophobic function based on the Silicone-Polyester copolymer resin of PET segment;
(2) Silicone-Polyester multipolymer compound substrate membranes of the present invention, its key point is received by hydrophobic grouping on the Silicone-Polyester copolymer resin molecular chain based on PET segment, utilize the hydrophobic function of hydrophobic grouping, thus improve effect of hydrolysis, make film PCT digestion time (test condition: 121 DEG C, 100%RH) bring up to 60h ~ 96h from current 40h ~ 60h;
(3) another function of Silicone-Polyester multipolymer compound substrate membranes of the present invention, utilize the function based on containing hydrophobic grouping in the Silicone-Polyester copolymer resin molecular chain of PET segment, thus reach the block-water performance improving its film, make pellicular water vapor transmission rates (test condition: 38 DEG C, 90%RH) from current 1.5g/m
224h ~ 2.0g/m
224h is reduced to 0.8g/m
224h ~ 1.2g/m
224h;
(4) Silicone-Polyester multipolymer compound substrate membranes of the present invention, by based on the function containing hydrophobic grouping in the Silicone-Polyester copolymer resin molecular chain of PET segment, makes the anti-hydrolytic performance of Silicone-Polyester multipolymer compound substrate membranes significantly improve; Silicone-Polyester multipolymer compound substrate membranes of the present invention 121 DEG C, after 2MPa high temperature steaming 60h ~ 96h, elongation at break remains on 25% ~ 50%;
(5) product preparation process of the present invention is simple, easily operates, and product performance are good, practical.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
The preparation of first part's Silicone-Polyester copolymer resin
Basic technology and raw material:
The preparation method of described Silicone-Polyester copolymer resin is: first got the raw materials ready by 1000mol terephthalic acid, again 1050mol ~ 1200mol being contained dihydroxy compound is ethylene glycol in molar ratio: prepare burden containing dimethylsiloxane compounds=800 ~ 950:100 ~ 400, add together in reactor, initial pressure 0.2MPa in reactor, when reactor temperature rises to 230 DEG C ~ 250 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start (slowly) pressure release, add catalyzer 0.13mol ~ 0.23mol antimonous oxide, stablizer 0.025mol ~ 0.036mol triphenylphosphate, stir 15min ~ 20min, then starting (slowly) vacuumizes, to reactor, overbottom pressure is less than 60Pa, and be warming up to 280 DEG C ~ 290 DEG C and carry out polycondensation, polycondensation time 3h ~ 4h, be filled with N
2discharging, namely obtained Silicone-Polyester copolymer resin, for subsequent use,
Describedly refer to a kind of or combination of two kinds of dialkyl polydimethylsiloxane (1*), hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane) (2*) containing dimethylsiloxane compounds;
The situations such as embodiment 1-1 ~ 1-8 processing parameter, material and consumption see the following form 1:
Table 1: processing parameter, material that embodiment is chosen and use scale
The preparation of second section Silicone-Polyester multipolymer compound substrate membranes
Basic technology and raw material:
Be that 10 ~ 200:100 gets the raw materials ready respectively in mass ratio by the Silicone-Polyester copolymer resin prepared in above-described embodiment and PET resin, and respectively by forcing machine A260 DEG C ~ 280 DEG C, at forcing machine B265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, compound slab on cold drum at 15 DEG C ~ 25 DEG C, compound slab again at 70 DEG C ~ 80 DEG C through 2.7 ~ 3.3 times of longitudinal stretchings, then 45 DEG C ~ 60 DEG C are cooled to through 1s ~ 5s, 2.8 ~ 3.4 times of cross directional stretchs are carried out again at 110 DEG C ~ 130 DEG C, film through two-way stretch enters electrically heated passage heat set zone, wherein the firstth district is 200 DEG C ~ 210 DEG C, secondth district is 210 DEG C ~ 215 DEG C, 3rd district is 215 DEG C ~ 220 DEG C, 4th district is 215 DEG C ~ 220 DEG C, 5th district is 225 DEG C ~ 230 DEG C, 6th district is 190 DEG C ~ 200 DEG C, film thermal shaping time is 8s ~ 120s, film through heat set zone again through 60 DEG C ~ 70 DEG C, the cooling in two stages under 6s ~ 20s and room temperature, rolling, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g;
The situations such as embodiment 2-1 ~ 2-8 processing parameter, material and consumption see the following form 2:
Table 2: processing parameter, material that embodiment is chosen and use scale
The capability and performance table of Part III Silicone-Polyester copolymer resin and compound substrate membranes
Table 3: the capability and performance table of Silicone-Polyester copolymer resin
Table 4: the capability and performance table of Silicone-Polyester multipolymer compound substrate membranes
Embodiment 3::
A kind of Silicone-Polyester copolymer resin, general formula of molecular structure is:
In formula:
or
wherein: m is 25 ~ 40, n be 10 ~ 20, X be 5 ~ 10, Y is 3 ~ 5, m, n, X and Y are integer;
The limiting viscosity of described Silicone-Polyester copolymer resin is 0.60dl/g ~ 0.68dl/g, and melting range is 240 DEG C ~ 253 DEG C, and molecular weight is 10000 ~ 25000;
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1050mol ~ 1200mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 230 DEG C ~ 250 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start (slowly) pressure release, add (catalyzer) 0.13mol ~ 0.23mol antimonous oxide, (stablizer) 0.025mol ~ 0.036mol triphenylphosphate, stir 15min ~ 20min, then starting (slowly) vacuumizes, to reactor, overbottom pressure is less than 60Pa, and be warming up to 280 DEG C ~ 290 DEG C and carry out polycondensation, polycondensation time 3h ~ 4h, be filled with N
2(nitrogen) discharging, i.e. obtained Silicone-Polyester copolymer resin,
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=800 ~ 950:100 ~ 400 ethylene glycol with contain dimethylsiloxane compounds and mix and form;
Described is one or both mixture in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane) containing dimethylsiloxane compounds.
Embodiment 4:
A kind of Silicone-Polyester multipolymer compound substrate membranes, be made up of the Silicone-Polyester copolymer film (being called for short: A layer) of A layer and PET film (being called for short: the B layer) compound of B layer, its laminate structure is that A/B is two-layer, thickness is 100 μm, the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 10:100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope;
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 10 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 260 DEG C, forcing machine B at temperature 265 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 15 DEG C, again through 2.8 times of longitudinal stretchings, 2.9 times of cross directional stretchs, heat setting type at temperature 190 DEG C, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes;
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Embodiment 5:
A kind of Silicone-Polyester multipolymer compound substrate membranes, be made up of the Silicone-Polyester copolymer film (being called for short: A layer) of A layer and PET film (being called for short: the B layer) compound of B layer, its laminate structure is that A/B is two-layer, thickness is 300 μm, the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 200:100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope;
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 200 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 280 DEG C, forcing machine B at temperature 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 25 DEG C, again through 3.3 times of longitudinal stretchings, 3.4 times of cross directional stretchs, heat setting type at temperature 190 DEG C ~ 230 DEG C, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes;
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Embodiment 6:
A kind of Silicone-Polyester multipolymer compound substrate membranes, be made up of the Silicone-Polyester copolymer film (being called for short: A layer) of A layer and PET film (being called for short: the B layer) compound of B layer, its laminate structure is that A/B is two-layer, thickness is 200 μm, the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 105:100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope;
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 105 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 270 DEG C, forcing machine B at temperature 280 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 20 DEG C, again through 3 times of longitudinal stretchings, 3.1 times of cross directional stretchs, heat setting type at temperature 210 DEG C, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes;
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Embodiment 7 ~ 12:
A kind of Silicone-Polyester multipolymer compound substrate membranes, be made up of the Silicone-Polyester copolymer film (being called for short: A layer) of A layer and PET film (being called for short: the B layer) compound of B layer, its laminate structure is that A/B is two-layer, thickness is 100 μm ~ 300 μm, and (thickness of embodiment 7 ~ 12 is respectively: 130 μm, 180 μm, 210 μm, 240 μm, 260 μm, 270 μm), the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is that 10 ~ 200 (embodiment 7 ~ 12 is respectively: 30, 60, 90, 120, 150, 180): 100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h, at 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope,
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by 10 ~ 200, (embodiment 7 ~ 12 is respectively: 30, 60, 90, 120, 150, 180) PET resin of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of mass parts A layer and the PET film of 100 mass parts B layers respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 15 DEG C ~ 25 DEG C, (embodiment 7 ~ 12 is respectively: 2.8 through 2.8 ~ 3.3 again, 2.9, 3, 3.1, 3.2, 3.3) times longitudinal stretching, 2.9 ~ 3.4 (embodiment 7 ~ 12 is respectively: 2.8, 2.9, 3, 3.1, 3.2, 3.3) times cross directional stretch, heat setting type at temperature 190 DEG C ~ 230 DEG C, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Embodiment 13:
A kind of Silicone-Polyester multipolymer compound substrate membranes, be made up of the PET film (be called for short: B layer) of B layer and the Silicone-Polyester copolymer film (abbreviation: A layer) of A layer on the PET film two sides that is compounded in B layer, its laminate structure is A/B/A tri-layers two kinds, thickness is 100 μm, the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 10:100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope;
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 10 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 260 DEG C, forcing machine B at temperature 265 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 15 DEG C, again through 2.8 times of longitudinal stretchings, 2.9 times of cross directional stretchs, heat setting type at temperature 190 DEG C and obtaining;
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Embodiment 14:
A kind of Silicone-Polyester multipolymer compound substrate membranes, be made up of the PET film (be called for short: B layer) of B layer and the Silicone-Polyester copolymer film (abbreviation: A layer) of A layer on the PET film two sides that is compounded in B layer, its laminate structure is A/B/A tri-layers two kinds, thickness is 300 μm, the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 200:100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope;
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 200 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 280 DEG C, forcing machine B at temperature 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 25 DEG C, again through 3.3 times of longitudinal stretchings, 3.4 times of cross directional stretchs, heat setting type at temperature 190 DEG C ~ 230 DEG C and obtaining;
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Embodiment 15:
A kind of Silicone-Polyester multipolymer compound substrate membranes, be made up of the PET film (be called for short: B layer) of B layer and the Silicone-Polyester copolymer film (abbreviation: A layer) of A layer on the PET film two sides that is compounded in B layer, its laminate structure is A/B/A tri-layers two kinds, thickness is 200 μm, the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 105:100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope;
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 105 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 270 DEG C, forcing machine B at temperature 275 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 20 DEG C, again through 3 times of longitudinal stretchings, 3.1 times of cross directional stretchs, heat setting type at temperature 210 DEG C and obtaining;
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Embodiment 16 ~ 21:
A kind of Silicone-Polyester multipolymer compound substrate membranes, be made up of the PET film (be called for short: B layer) of B layer and the Silicone-Polyester copolymer film (abbreviation: A layer) of A layer on the PET film two sides that is compounded in B layer, its laminate structure is A/B/A tri-layers two kinds, thickness is 100 μm ~ 300 μm, and (thickness of embodiment 16 ~ 21 is respectively: 130 μm, 180 μm, 210 μm, 240 μm, 260 μm, 270 μm), the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is that 10 ~ 200 (embodiment 16 ~ 21 is respectively: 30, 60, 90, 120, 150, 180): 100, the anti-hydrolytic performance of described Silicone-Polyester multipolymer compound substrate membranes is: when 121 DEG C of (high temperature) boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h, at 38 DEG C, under 90%RH (RH is RelativeHumidity, i.e. relative humidity) test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope,
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by 10 ~ 200, (embodiment 16 ~ 21 is respectively: 30, 60, 90, 120, 150, 180) PET resin of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of mass parts A layer and the PET film of 100 mass parts B layers respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 15 DEG C ~ 25 DEG C, (embodiment 16 ~ 21 is respectively: 2.8 through 2.8 ~ 3.3 again, 2.9, 3, 3.1, 3.2, 3.3) times longitudinal stretching, 2.9 ~ 3.4 (embodiment 16 ~ 21 is respectively: 2.8, 2.9, 3, 3.1, 3.2, 3.3) times cross directional stretch, heat setting type at temperature 190 DEG C ~ 230 DEG C and obtaining,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g.
Embodiment 22:
A preparation method for Silicone-Polyester multipolymer compound substrate membranes, step is:
A, prepare silicone-containing-polyethylene terephthalate copolymer resin:
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1050mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 230 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start (slowly) pressure release, add (catalyzer) 0.13mol antimonous oxide, (stablizer) 0.025mol triphenylphosphate, stir 15min, then starting (slowly) vacuumizes, to reactor, overbottom pressure is less than 60Pa, and be warming up to 280 DEG C and carry out polycondensation, polycondensation time 3h, be filled with N
2discharging, namely obtained Silicone-Polyester copolymer resin, for subsequent use,
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=800:250 ethylene glycol with contain dimethylsiloxane compounds and mix and form;
Described one or both the mixture referred to containing dimethylsiloxane compounds in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane);
B, prepare Silicone-Polyester multipolymer compound substrate membranes:
The Silicone-Polyester copolymer resin prepared by step a and PET resin are got the raw materials ready respectively for 10:100 in mass ratio, and respectively by forcing machine A in temperature 260 DEG C, forcing machine B is at temperature 265 DEG C after melting, extrude through resin melting divider layering co-extrusion, compound slab on cold drum at temperature 15 DEG C, compound slab again under temperature 70 C through 2.7 times of longitudinal stretchings, then temperature 45 C is cooled to through 1s, 2.8 times of cross directional stretchs are carried out again at temperature 110 DEG C, film through two-way stretch enters electrically heated passage heat set zone, wherein first district's temperature is 200 DEG C, secondth district is 210 DEG C, 3rd district is 215 DEG C, 4th district is 215 DEG C, 5th district is 225 DEG C, 6th district is 190 DEG C, film thermal shaping time is 8s, the cooling in two stages under temperature 60 C, time 6s and room temperature again of film through heat set zone, rolling, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g;
The thickness of described Silicone-Polyester multipolymer compound substrate membranes is 100 μm, and anti-hydrolytic performance is: when 121 DEG C of boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope.
Embodiment 23:
A preparation method for Silicone-Polyester multipolymer compound substrate membranes, step is:
A, prepare silicone-containing-polyethylene terephthalate copolymer resin:
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1200mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 250 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start (slowly) pressure release, add (catalyzer) 0.23mol antimonous oxide, (stablizer) 0.036mol triphenylphosphate, stir 20min, then starting (slowly) vacuumizes, to reactor, overbottom pressure is less than 60Pa, and be warming up to 290 DEG C and carry out polycondensation, polycondensation time 4h, be filled with N
2discharging, namely obtained Silicone-Polyester copolymer resin, for subsequent use,
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=950:250 ethylene glycol with contain dimethylsiloxane compounds and mix and form;
Described one or both the mixture referred to containing dimethylsiloxane compounds in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane);
B, prepare Silicone-Polyester multipolymer compound substrate membranes:
The Silicone-Polyester copolymer resin prepared by step a and PET resin are got the raw materials ready respectively for 200:100 in mass ratio, and respectively by forcing machine A in temperature 280 DEG C, forcing machine B is at temperature 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, compound slab on cold drum at temperature 25 DEG C, compound slab again at temperature 80 DEG C through 3.3 times of longitudinal stretchings, then temperature 60 C is cooled to through 5s, 3.4 times of cross directional stretchs are carried out again at temperature 130 DEG C, film through two-way stretch enters electrically heated passage heat set zone, wherein first district's temperature is 210 DEG C, secondth district is 215 DEG C, 3rd district is 220 DEG C, 4th district is 220 DEG C, 5th district is 230 DEG C, 6th district is 200 DEG C, film thermal shaping time is 120s, the cooling in two stages under temperature 70 C, time 20s and room temperature again of film through heat set zone, rolling, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g;
The thickness of described Silicone-Polyester multipolymer compound substrate membranes is 300 μm, and anti-hydrolytic performance is: when 121 DEG C of boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope.
Embodiment 24:
A preparation method for Silicone-Polyester multipolymer compound substrate membranes, step is:
A, prepare silicone-containing-polyethylene terephthalate copolymer resin:
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1100mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 240 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start (slowly) pressure release, add (catalyzer) 0.18mol antimonous oxide, (stablizer) 0.03mol triphenylphosphate, stir 18min, then starting (slowly) vacuumizes, to reactor, overbottom pressure is less than 60Pa, and be warming up to 285 DEG C and carry out polycondensation, polycondensation time 3.5h, be filled with N
2discharging, namely obtained Silicone-Polyester copolymer resin, for subsequent use,
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=900:200 ethylene glycol with contain dimethylsiloxane compounds and mix and form;
Described one or both the mixture referred to containing dimethylsiloxane compounds in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane);
B, prepare Silicone-Polyester multipolymer compound substrate membranes:
The Silicone-Polyester copolymer resin prepared by step a and PET resin are got the raw materials ready respectively for 105:100 in mass ratio, and respectively by forcing machine A in temperature 270 DEG C, forcing machine B is at temperature 280 DEG C after melting, extrude through resin melting divider layering co-extrusion, compound slab on cold drum at temperature 20 DEG C, compound slab again at temperature 75 DEG C through 3 times of longitudinal stretchings, then temperature 52 DEG C is cooled to through 3s, 3.1 times of cross directional stretchs are carried out again at temperature 120 DEG C, film through two-way stretch enters electrically heated passage heat set zone, wherein first district's temperature is 205 DEG C, secondth district is 213 DEG C, 3rd district is 218 DEG C, 4th district is 218 DEG C, 5th district is 228 DEG C, 6th district is 195 DEG C, film thermal shaping time is 64s, the cooling in two stages under temperature 65 DEG C, time 13s and room temperature again of film through heat set zone, rolling, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g;
The thickness of described Silicone-Polyester multipolymer compound substrate membranes is 200 μm, and anti-hydrolytic performance is: when 121 DEG C of boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope.
Embodiment 25 ~ 31:
A preparation method for Silicone-Polyester multipolymer compound substrate membranes, step is:
A, prepare silicone-containing-polyethylene terephthalate copolymer resin:
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1050mol ~ 1200mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 230 DEG C ~ 250 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start (slowly) pressure release, add (catalyzer) 0.13mol ~ 0.23mol antimonous oxide, (stablizer) 0.025mol ~ 0.036mol triphenylphosphate, stir 15min ~ 20min, then starting (slowly) vacuumizes, to reactor, overbottom pressure is less than 60Pa, and be warming up to 280 DEG C ~ 290 DEG C and carry out polycondensation, polycondensation time 3h ~ 4h, be filled with N
2discharging, namely obtained Silicone-Polyester copolymer resin, for subsequent use, concrete mole of (mol) consumption of each component in embodiment 25 ~ 31 sees the following form:
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=800 ~ 950:100 ~ 400 ethylene glycol with contain dimethylsiloxane compounds and mix and form; Concrete mole of (mol) consumption of each component in embodiment 25 ~ 31 sees the following form:
Described one or both the mixture referred to containing dimethylsiloxane compounds in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane);
B, prepare Silicone-Polyester multipolymer compound substrate membranes:
The Silicone-Polyester copolymer resin prepared by step a and PET resin are that 10 ~ 200 (embodiment 25 ~ 31 is respectively: 30 in mass ratio, 60, 90, 120, 150, 180, 190): 100 get the raw materials ready respectively, and respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, compound slab on cold drum at temperature 15 DEG C ~ 25 DEG C, at temperature 70 C ~ 80 DEG C, (embodiment 25 ~ 31 is respectively compound slab: 2.7 through 2.7 ~ 3.3 again, 2.8, 2.9, 3, 3.1, 3.2, 3.3) times longitudinal stretching, then be cooled to temperature 45 C ~ 60 DEG C through 1s ~ 5s, then at temperature 110 DEG C ~ 130 DEG C, carrying out 2.8 ~ 3.4, (embodiment 25 ~ 31 is respectively: 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4) times cross directional stretch, the film through two-way stretch enters electrically heated passage heat set zone, and wherein first district's temperature is 200 DEG C ~ 210 DEG C, secondth district is 210 DEG C ~ 215 DEG C, 3rd district is 215 DEG C ~ 220 DEG C, 4th district is 215 DEG C ~ 220 DEG C, 5th district is 225 DEG C ~ 230 DEG C, 6th district is 190 DEG C ~ 200 DEG C, and film thermal shaping time is 8s ~ 120s, the cooling in two stages under temperature 60 C ~ 70 DEG C, time 6s ~ 20s and room temperature again of film through heat set zone, rolling, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes,
Described PET resin is commercially available limiting viscosity is the PET resin of 0.60dl/g ~ 0.68dl/g;
The thickness of described Silicone-Polyester multipolymer compound substrate membranes is 100 μm ~ 300 μm (thickness of embodiment 25 ~ 31 is respectively: 130 μm, 180 μm, 210 μm, 240 μm, 260 μm, 270 μm, 285 μm), anti-hydrolytic performance is: when 121 DEG C of boilings make elongation at break decay to 10%, cooking time reaches 60h ~ 96h; At 38 DEG C, under 90%RH test environment, water vapor transmission rate (WVTR) is at 0.8g/m
224h ~ 1.2g/m
2in 24h scope.
In above-described embodiment 22 ~ 31: the Silicone-Polyester multipolymer compound substrate membranes that step b obtains is A/B two laminate or A/B/A tri-laminate.
In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage or well known to a person skilled in the art percentage; In the ratio adopted, do not indicate especially, be quality (weight) ratio; Described weight part can be all gram or kilogram.
In above-described embodiment: the processing parameter (temperature, time, concentration etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment, described starting material are commercially available prod.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (6)
1. a Silicone-Polyester copolymer resin, is characterized in that: the general formula of molecular structure of described Silicone-Polyester copolymer resin is:
In formula: R
1=
or R
1=
wherein: m is 25 ~ 40, n be 10 ~ 20, X be 5 ~ 10, Y is 3 ~ 5, m, n, X and Y are integer;
The molecular weight of described Silicone-Polyester copolymer resin is 10000 ~ 25000;
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1050mol ~ 1200mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 230 DEG C ~ 250 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start pressure release, add 0.13mol ~ 0.23mol antimonous oxide, 0.025mol ~ 0.036mol triphenylphosphate, stir 15min ~ 20min, then start to vacuumize, to reactor, overbottom pressure is less than 60Pa, and be warming up to 280 DEG C ~ 290 DEG C and carry out polycondensation, polycondensation time 3h ~ 4h, be filled with N
2discharging, i.e. obtained Silicone-Polyester copolymer resin,
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=800 ~ 950:100 ~ 400 ethylene glycol with contain dimethylsiloxane compounds and mix and form;
Described is one or both mixture in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane) containing dimethylsiloxane compounds.
2. a Silicone-Polyester multipolymer compound substrate membranes, it is characterized in that: described Silicone-Polyester multipolymer compound substrate membranes is made up of the Silicone-Polyester copolymer film of A layer and the PET film compound of B layer, thickness is 100 μm ~ 300 μm, and the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 10 ~ 200:100;
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 10 ~ 200 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 15 DEG C ~ 25 DEG C, again through 2.8 ~ 3.3 times of longitudinal stretchings, 2.9 ~ 3.4 times of cross directional stretchs, heat setting type at temperature 190 DEG C ~ 230 DEG C, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes.
3. a Silicone-Polyester multipolymer compound substrate membranes, it is characterized in that: described Silicone-Polyester multipolymer compound substrate membranes is made up of the PET film of B layer and the Silicone-Polyester copolymer film of A layer on the PET film two sides that is compounded in B layer, thickness is 100 μm ~ 300 μm, and the mass ratio of the Silicone-Polyester copolymer film of A layer and the PET film of B layer is 10 ~ 200:100;
The preparation method of described Silicone-Polyester multipolymer compound substrate membranes is: by the PET resin of the PET film of the Silicone-Polyester copolymer resin of the Silicone-Polyester copolymer film of 10 ~ 200 mass parts A layers and 100 mass parts B layers respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, slab on cold drum at temperature 15 DEG C ~ 25 DEG C, again through 2.8 ~ 3.3 times of longitudinal stretchings, 2.9 ~ 3.4 times of cross directional stretchs, heat setting type at temperature 190 DEG C ~ 230 DEG C and obtaining.
4. a preparation method for Silicone-Polyester multipolymer compound substrate membranes, is characterized in that step is:
A, prepare silicone-containing-polyethylene terephthalate copolymer resin:
The preparation method of described Silicone-Polyester copolymer resin is: add in reactor by 1000mol terephthalic acid and 1050mol ~ 1200mol containing dihydroxy compound, initial pressure 0.2MPa in reactor, when reactor temperature rises to 230 DEG C ~ 250 DEG C, collect esterification and distillate moisture, esterification yield is calculated by aquifer yield, when esterification yield reaches 97%, start pressure release, add 0.13mol ~ 0.23mol antimonous oxide, 0.025mol ~ 0.036mol triphenylphosphate, stir 15min ~ 20min, then start to vacuumize, to reactor, overbottom pressure is less than 60Pa, and be warming up to 280 DEG C ~ 290 DEG C and carry out polycondensation, polycondensation time 3h ~ 4h, be filled with N
2discharging, namely obtained Silicone-Polyester copolymer resin, for subsequent use,
Described is ethylene glycol containing dihydroxy compound by mol ratio: containing dimethylsiloxane compounds=800 ~ 950:100 ~ 400 ethylene glycol with contain dimethylsiloxane compounds and mix and form;
Described one or both the mixture referred to containing dimethylsiloxane compounds in dialkyl polydimethylsiloxane, hydroxy-end capped methyl-3,3,3-trifluoro propyl (siloxanes and polysiloxane);
B, prepare Silicone-Polyester multipolymer compound substrate membranes:
The Silicone-Polyester copolymer resin prepared by step a and PET resin are that 10 ~ 200:100 gets the raw materials ready respectively in mass ratio, and respectively by forcing machine A in temperature 260 DEG C ~ 280 DEG C, forcing machine B is at temperature 265 DEG C ~ 290 DEG C after melting, extrude through resin melting divider layering co-extrusion, compound slab on cold drum at temperature 15 DEG C ~ 25 DEG C, compound slab again at temperature 70 C ~ 80 DEG C through 2.7 ~ 3.3 times of longitudinal stretchings, then temperature 45 C ~ 60 DEG C are cooled to through 1s ~ 5s, 2.8 ~ 3.4 times of cross directional stretchs are carried out again at temperature 110 DEG C ~ 130 DEG C, film through two-way stretch enters electrically heated passage heat set zone, wherein first district's temperature is 200 DEG C ~ 210 DEG C, secondth district is 210 DEG C ~ 215 DEG C, 3rd district is 215 DEG C ~ 220 DEG C, 4th district is 215 DEG C ~ 220 DEG C, 5th district is 225 DEG C ~ 230 DEG C, 6th district is 190 DEG C ~ 200 DEG C, film thermal shaping time is 8s ~ 120s, the cooling in two stages under temperature 60 C ~ 70 DEG C, time 6s ~ 20s and room temperature again of film through heat set zone, rolling, i.e. obtained Silicone-Polyester multipolymer compound substrate membranes.
5., by the preparation method of Silicone-Polyester multipolymer compound substrate membranes described in claim 4, it is characterized in that: the thickness of described obtained Silicone-Polyester multipolymer compound substrate membranes is 100 μm ~ 300 μm.
6. by the preparation method of Silicone-Polyester multipolymer compound substrate membranes described in claim 4 or 5, it is characterized in that: the Silicone-Polyester multipolymer compound substrate membranes that step b obtains is A/B two laminate or A/B/A tri-laminate.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565943A (en) * | 2016-11-08 | 2017-04-19 | 四川东材科技集团股份有限公司 | Fluorosilicone copolyester resin and preparing method thereof |
| CN106832240A (en) * | 2017-01-16 | 2017-06-13 | 哈尔滨工业大学无锡新材料研究院 | With PET mould release membrances from release function and preparation method thereof |
| WO2019062428A1 (en) * | 2017-09-27 | 2019-04-04 | 南通星辰合成材料有限公司 | Polyester segmented copolymer and preparation method therefor and application thereof |
| CN110713700A (en) * | 2018-07-13 | 2020-01-21 | 南通星辰合成材料有限公司 | Polyester composite material and preparation method and application thereof |
| CN113444235A (en) * | 2020-05-06 | 2021-09-28 | 广东虹勤通讯技术有限公司 | Modified PCT resin, preparation method thereof and resin alloy material |
| CN113501948A (en) * | 2021-07-26 | 2021-10-15 | 智谱纳米科技(上海)有限公司 | Polyester hydrophobic master batch and preparation method and application thereof |
| CN113668092A (en) * | 2021-10-25 | 2021-11-19 | 苏州宝丽迪材料科技股份有限公司 | Polyester fiber and method for producing same |
| CN114933697A (en) * | 2022-02-28 | 2022-08-23 | 天津天达联合工程技术有限公司 | Biodegradable copolyester and preparation method and application thereof |
| CN115612080A (en) * | 2021-07-14 | 2023-01-17 | 华润化学材料科技股份有限公司 | Silicon-containing polyester and preparation method thereof |
| CN116333465A (en) * | 2023-05-23 | 2023-06-27 | 北京助天科技集团有限公司 | Novel organic-inorganic composite material, preparation method and application thereof |
| CN117887262A (en) * | 2023-12-25 | 2024-04-16 | 浙江凌志新能源科技有限公司 | Organic silicon material for liquid cooling support of power battery and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565943A (en) * | 2016-11-08 | 2017-04-19 | 四川东材科技集团股份有限公司 | Fluorosilicone copolyester resin and preparing method thereof |
| CN106832240A (en) * | 2017-01-16 | 2017-06-13 | 哈尔滨工业大学无锡新材料研究院 | With PET mould release membrances from release function and preparation method thereof |
| WO2019062428A1 (en) * | 2017-09-27 | 2019-04-04 | 南通星辰合成材料有限公司 | Polyester segmented copolymer and preparation method therefor and application thereof |
| CN110713700A (en) * | 2018-07-13 | 2020-01-21 | 南通星辰合成材料有限公司 | Polyester composite material and preparation method and application thereof |
| CN113444235A (en) * | 2020-05-06 | 2021-09-28 | 广东虹勤通讯技术有限公司 | Modified PCT resin, preparation method thereof and resin alloy material |
| CN115612080A (en) * | 2021-07-14 | 2023-01-17 | 华润化学材料科技股份有限公司 | Silicon-containing polyester and preparation method thereof |
| CN113501948A (en) * | 2021-07-26 | 2021-10-15 | 智谱纳米科技(上海)有限公司 | Polyester hydrophobic master batch and preparation method and application thereof |
| CN113668092A (en) * | 2021-10-25 | 2021-11-19 | 苏州宝丽迪材料科技股份有限公司 | Polyester fiber and method for producing same |
| CN114933697A (en) * | 2022-02-28 | 2022-08-23 | 天津天达联合工程技术有限公司 | Biodegradable copolyester and preparation method and application thereof |
| CN116333465A (en) * | 2023-05-23 | 2023-06-27 | 北京助天科技集团有限公司 | Novel organic-inorganic composite material, preparation method and application thereof |
| CN116333465B (en) * | 2023-05-23 | 2023-08-08 | 北京助天科技集团有限公司 | Organic-inorganic composite material, preparation method and application thereof |
| CN117887262A (en) * | 2023-12-25 | 2024-04-16 | 浙江凌志新能源科技有限公司 | Organic silicon material for liquid cooling support of power battery and preparation method |
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