CN108431078A - 含1,4:3,6-双脱水己糖醇和各种环状二醇的芳香族热塑性共聚酯 - Google Patents
含1,4:3,6-双脱水己糖醇和各种环状二醇的芳香族热塑性共聚酯 Download PDFInfo
- Publication number
- CN108431078A CN108431078A CN201680070741.4A CN201680070741A CN108431078A CN 108431078 A CN108431078 A CN 108431078A CN 201680070741 A CN201680070741 A CN 201680070741A CN 108431078 A CN108431078 A CN 108431078A
- Authority
- CN
- China
- Prior art keywords
- polyester
- bis
- unit
- advantageously
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- 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
-
- 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
- B32B27/08—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 synthetic resin
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
-
- 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
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
- C08G63/197—Hydroxy compounds containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
- B32B2262/062—Cellulose fibres, e.g. cotton
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
- B32B2262/062—Cellulose fibres, e.g. cotton
- B32B2262/065—Lignocellulosic fibres, e.g. jute, sisal, hemp, flax, bamboo
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
- B32B2262/062—Cellulose fibres, e.g. cotton
- B32B2262/067—Wood fibres
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/101—Glass
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
-
- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- 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
- B32B2307/21—Anti-static
-
- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/414—Translucent
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
-
- 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
-
- 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
- B32B2307/536—Hardness
-
- 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
- B32B2307/558—Impact strength, toughness
-
- 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
- B32B2307/70—Other properties
- B32B2307/702—Amorphous
-
- 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
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
-
- 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
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
-
- 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
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
-
- 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
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- 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
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
-
- 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
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
-
- 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
- B32B2551/00—Optical elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2250/00—Compositions for preparing crystalline polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明涉及一种热塑性聚酯,其包含:至少一种1,4:3,6‑双脱水己糖醇单元(A);至少一种除了环己烷二甲醇单元和1,4:3,6‑双脱水己糖醇单元(A)以外的环状二醇单元(B);和至少一种芳香族二羧酸单元(C),所述聚酯不含乙二醇单元。本发明还涉及其生产方法和用途。
Description
技术领域
本发明涉及不含乙二醇单元并具有高的1,4:3,6-双脱水己糖醇单元掺入程度的热塑性聚酯。本发明的另一主题是一种用于生产所述聚酯的方法以及该聚酯用于生产各种光学制品的用途。
发明的技术背景
光学玻璃和透明光学树脂被用于制造各种光学装置(例如像照相机、电影摄影机、望远镜、放大镜、双筒望远镜或投影仪)中的光学透镜。透明光学树脂还具有呈光学膜形式的应用,例如用于电子装置的屏幕。
光学玻璃具有优异的耐热性、透明度、尺寸稳定性和耐化学性的特性。但是,它的成本价格高并且不能或者只能很难地通过模制来转化。与光学玻璃不同,由透明光学树脂、特别是透明热塑性树脂制造的透镜具有以下优点:它可以通过注射模制容易地大量生产。
透明光学树脂的实例尤其包括聚碳酸酯和聚(甲基丙烯酸甲酯)(PMMA)。但是,这些树脂有几个缺点。聚碳酸酯的高粘度在其形成方面造成问题。此外,聚碳酸酯具有有限的耐UV辐射性。关于聚(甲基丙烯酸甲酯),由于其低耐热性,其在经受高温的光学应用(例如像投影仪透镜或电子装置的屏幕)中具有限制。
因此,目前仍然需要寻找新颖的透明树脂,这些树脂具有可以容易地形成且具有高冲击强度以及还有耐热性的有利的光学特性。
值得称道的是,申请人已发现了该目标可以用包含以下项的热塑性聚酯来实现:1,4:3,6-双脱水己糖醇单元;以及除了环己烷二甲醇单元和所述1,4:3,6-双脱水己糖醇单元以外的环状二醇单元。
发明内容
因此,本发明的主题是一种热塑性聚酯,其包含:
●至少一种1,4:3,6-双脱水己糖醇单元(A);
●至少一种除了环己烷二甲醇单元和所述1,4:3,6-双脱水己糖醇单元(A)以外的环状二醇单元(B);
●至少一种芳香族二羧酸单元(C);
所述聚酯不含乙二醇单元。
该聚合物尤其可以通过特定的生产方法获得,所述方法尤其包括将单体引入反应器的步骤,所述单体包含至少一种1,4:3,6-双脱水己糖醇(A),至少一种除了环己烷二甲醇和所述1,4:3,6-双脱水己糖醇(A)以外的环状二醇(B)和至少一种芳香族二羧酸(C),所述单体不含乙二醇。
该方法包括在催化体系存在下且在高温下聚合所述单体以形成该聚酯的步骤,所述步骤由以下组成:
■低聚的第一阶段,在该第一阶段期间,首先将反应介质在惰性气氛下在范围从150℃至250℃、有利地从170℃至240℃、更有利地从180℃至235℃的温度下进行搅拌,然后使其达到范围从230℃至300℃、有利地范围从240℃至290℃、更有利地从245℃至270℃的温度;
■低聚物缩合的第二阶段,在该第二阶段期间,在真空下在范围从240℃至320℃、有利地从275℃至310℃、更有利地从289℃至310℃的温度下搅拌所形成的低聚物以便形成该聚酯;以及
回收该聚酯的步骤。
与所有预期相反,申请人已经观察到,通过不使用乙二醇作为二醇单体,可以获得具有高玻璃化转变温度的新颖的热塑性聚酯。这可以通过以下事实解释:乙二醇的反应动力学比1,4:3,6-双脱水己糖醇的反应动力学快得多,这极大地限制了后者结合到聚酯中。由此得到的聚酯因此具有低的1,4:3,6-双脱水己糖醇结合度以及因此相对低的玻璃化转变温度。
由于不存在乙二醇单元,根据本发明的聚酯具有高玻璃化转变温度,并且可以用于许多用于转化塑料材料的工具中,并且特别是可以通过模制、尤其是注射模制容易地转化。它还具有有利的光学特性,使得可以制造相对于常规聚酯具有高折射率和高阿贝数(折射率随波长的变化)的光学透镜。此外,其高玻璃化转变温度使其特别适用于经受高温的光学领域中的应用。
此外,根据本发明的聚酯具有有利的光学特性,特别是在其透光率、折射率和阿贝数方面。事实上,它们的特征为高透明度和高折射率以及更高的阿贝数(相比于常规聚酯)。
具体实施方式
为本发明的主题的聚合物是一种热塑性聚酯,其包含:
●至少一种1,4:3,6-双脱水己糖醇单元(A);
●至少一种除了环己烷二甲醇单元和所述1,4:3,6-双脱水己糖醇单元(A)以外的环状二醇单元(B);
●至少一种芳香族二羧酸单元(C);
所述聚酯不含乙二醇单元。
如上所解释,根据本发明的聚酯具有高玻璃化转变温度。有利的是,它具有至少95℃、优选至少100℃、更优先至少110℃并且更优先还至少120℃的玻璃化转变温度。在具体的实施例中,根据本发明的聚酯具有范围从95℃至155℃、优选从100℃至150℃、更优先从110℃至147℃、更优先还从120℃至145℃的玻璃化转变温度。
玻璃化转变温度通过常规方法、尤其使用差示扫描量热法(DSC)、使用10℃/min的加热速率测量。在以下实例部分中详细地描述了实验方案。
根据本发明的聚酯有利地具有大于88%、优选大于90%的透光率。
有利地,根据本发明的聚酯具有小于2%、优选小于1%的雾度。
在由根据本发明的聚酯制成的注射部件上根据方法ASTM D1003和ASTM D1003-95测量样品的雾度和透光率。
根据本发明的聚酯的折射率优选大于1.50,更优先大于1.55。它可以在厚的注射部件(例如3mm厚)上测量。然后在589nm(钠D线)下测量折射率。
根据本发明的聚酯的阿贝数优选大于30,更优先大于50。
根据下面的公式从在589nm(nD:钠D线)、486nm(nF:氢F线)和656nm(nC:氢C线)下获得的三个折射率测量结果计算阿贝数。
有利地,根据本发明的聚酯具有高冲击强度。优选地,在室温下测量的根据本发明的聚酯的冲击强度对于无缺口测试样本大于100kJ/m2,并且对于有缺口测试样本大于5kJ/m2。它可以通过根据标准ISO 179的夏比冲击测试的方式来评估(无缺口:ISO 179 1eU,有缺口:ISO 179 1eA)。
单元(A)是1,4:3,6-双脱水己糖醇单元。如前所解释,1,4:3,6-双脱水己糖醇具有在聚酯的生产中不是非常反应性的仲二醇的缺点。该1,4:3,6-双脱水己糖醇(A)可以是异山梨醇、异甘露醇、异艾杜糖醇、或其混合物。优选地,该1,4:3,6-双脱水己糖醇(A)是异山梨醇。
异山梨醇、异甘露醇和异艾杜糖醇分别可以通过山梨醇、甘露醇和艾杜糖醇的脱水获得。关于异山梨醇,它由本申请人以商标名P出售。
根据本发明的聚酯优选具有,相对于该聚酯中存在的所有二醇单元,至少1%、优选至少2%、更优先至少5%、并且更优先还至少10%的1,4:3,6-双脱水己糖醇单元(A)。
该聚酯中1,4:3,6-双脱水己糖醇单元(A)的量可以通过1H NMR或通过对从该聚酯的完全水解或甲醇分解得到的单体混合物进行色谱分析来确定,优选通过1H NMR。
本领域技术人员可以容易地找到用于确定聚酯的1,4:3,6-双脱水己糖醇单元(A)的量的分析条件。例如,从聚(螺环二醇-共-异山梨醇对苯二甲酸酯)的NMR光谱,关于螺环二醇的化学位移是在0.7ppm与0.9ppm之间、3.1ppm与3.6ppm以及4.1ppm与4.3ppm之间,并且关于异山梨醇的化学位移是在4.1ppm与5.8ppm之间。每个信号的积分使得可能确定一种单元相对于所有这两种二醇单元的相对量。
该环状二醇(B)可以选自螺环二醇、三环[5.2.1.02,6]癸烷二甲醇(TCDDM)、2,2,4,4-四甲基-1,3-环丁二醇、四氢呋喃二甲醇(THFDM)、呋喃-二甲醇、1,2-环戊二醇、1,3-环戊二醇、1,2-环己二醇、1,4-环己二醇、1,2-环庚二醇、1,5-萘二酚、2,7-萘二酚、1,4-萘二酚、2,3-萘二酚、2-甲基-1,4-萘二酚、1,4-苯二酚、八氢萘-4,8-二醇、二噁烷二醇(DOG)、降冰片烷二醇、金刚烷二醇和五环十五烷二甲醇。
在优选的实施例中,环状二醇(B)是螺环二醇、三环[5.2.1.02,6]癸烷二甲醇(TCDDM)或这两种二醇的混合物。
有利地,根据本发明的聚酯不含环己烷二甲醇单元。
芳香族二羧酸单元(C)有利地选自对苯二甲酸、2,5-呋喃二甲酸、2,6-萘二甲酸或间苯二甲酸单元以及这些酸单元中的两种或更多种的混合物。
根据一个实施例,根据本发明的聚酯仅包含一种类型的芳香族二羧酸单元。换句话说,根据该实施例,本发明的聚酯有利地含有至少一个对苯二甲酸单元、至少一个2,5-呋喃二甲酸单元或至少一个2,6-萘二甲酸单元或至少一个间苯二甲酸单元。
有利地,根据本发明的聚酯具有大于40ml/g、优选大于45ml/g、并且更优先大于50ml/g的溶液中比浓粘度。使用Ubbelohde毛细管粘度计在35℃下评估溶液中比浓粘度。在磁力搅拌下,在130℃下,将聚合物预先溶解在邻氯苯酚中。对于这些测量而言,引入的聚合物浓度是5g/l。
本发明的聚酯可以例如包含:
●在从5%至45%范围内的摩尔量的1,4:3,6-双脱水己糖醇单元(A);
●在从3%至47%范围内的摩尔量的除了环己烷二甲醇单元和所述1,4:3,6-双脱水己糖醇单元(A)以外的环状二醇单元(B);
●在从48%至52%范围内的摩尔量的二羧酸单元(C)。
聚酯中不同单元的量可以通过1H NMR或通过对从该聚酯的完全水解或甲醇分解得到的单体混合物进行色谱分析来确定,优选通过1H NMR。
本领域技术人员可以容易地找到用于确定该聚酯的单元的各自量的分析条件。例如,从聚(螺环二醇-共-异山梨醇对苯二甲酸酯)的NMR光谱,关于螺环二醇的化学位移是在0.7ppm与0.9ppm之间、在3.1ppm与3.6ppm之间和在4.1ppm与4.3ppm之间,关于对苯二甲酸酯环的化学位移是在7.8ppm与8.4ppm之间,并且关于异山梨醇的化学位移是在4.1ppm与5.8ppm之间。每个信号的积分使得可能确定该聚酯的每个单元的量。
根据本发明的聚酯可以是半结晶的或无定形的。
当根据本发明的聚酯是半结晶的时,其有利地具有范围从175℃至250℃、优选从190℃至220℃,例如从195℃至215℃的结晶温度。
优选地,当根据本发明的聚酯是半结晶的时,其具有范围从210℃至320℃,例如从225℃至310℃的熔点。
结晶温度和熔点通过常规方法、尤其使用差示扫描量热法(DSC)、使用10℃/min的加热速率测量。在以下实例部分中详细地描述了实验方案。
本发明的另一主题是一种用于生产根据本发明的聚酯的方法。这种方法包括:
●将单体引入反应器的步骤,所述单体包含至少一种1,4:3,6-双脱水己糖醇(A),至少一种除了所述1,4:3,6-双脱水己糖醇(A)以外的脂环族二醇(B)和至少一种二羧酸(C),所述单体不含乙二醇;
●将催化体系引入该反应器中的步骤;
●聚合所述单体以形成该聚酯的步骤,所述步骤由以下各项组成:
■低聚的第一阶段,在该第一阶段期间,首先将反应介质在惰性气氛下在范围从150℃至250℃、有利地从170℃至240℃、更有利地从180℃至235℃的温度下进行搅拌,然后使其达到范围从230℃至300℃、有利地范围从240℃至290℃、更有利地从245℃至270℃的温度;
■低聚物缩合的第二阶段,在该第二阶段期间,在真空下在范围从240℃至320℃、有利地从275℃至310℃、更有利地从289℃至310℃的温度下搅拌所形成的低聚物以便形成该聚酯;
●回收该聚酯的步骤。
如果根据本发明的聚酯是半结晶的,该方法可以包括以下步骤:在真空下或在用惰性气体例如像氮气(N2)冲洗时并且在比该聚酯的熔点低5℃至30℃的温度下进行固态后缩合。
催化体系旨在意指任选地分散或固定在惰性载体上的催化剂或催化剂的混合物。
该催化体系有利地选自下组,该组由以下各项组成:锡衍生物,优先锡、钛、锆、锗、锑、铋、铪、镁、铈、锌、钴、铁、锰、钙、锶、钠、钾、铝或锂的衍生物,或这些催化剂中的两种或更多种的混合物。这样的化合物的实例可以例如是在专利EP 1882 712 B1中在第[0090]至[0094]段中给出的那些。
该催化剂优选为锡、钛、锗、铝或锑的衍生物,更优先为锡的衍生物或锗的衍生物,例如二氧化二丁基锡或氧化锗。
催化体系以通常用于生产芳香族聚酯的催化量使用。通过按重量计的量的实例,相对于引入的单体的量,在低聚物缩合阶段期间可以使用从10至500ppm的催化体系。
根据本发明的方法,在单体的聚合步骤期间有利地使用抗氧化剂。这些抗氧化剂使得有可能减少所得聚酯的着色。抗氧化剂可以是主和/或辅助抗氧化剂。该主抗氧化剂可以是位阻酚,例如化合物0 3、0 10、0 16、210、276、10、76、3114、1010或1076或膦酸盐如195。该辅助抗氧化剂可以是三价磷化合物,如626、S-9228、P-EPQ或Irgafos 168。
还可能的是将至少一种能够限制不需要的醚化反应的化合物(如乙酸钠、四甲基氢氧化铵或四乙基氢氧化铵)作为聚合添加剂引入到该反应器内。
本发明的方法包括回收由聚合步骤得到的聚酯的步骤。该聚酯可以通过从该反应器中提取以熔融聚合物棒的形式的该组合物而回收。可以使用常规造粒技术将该棒转化为颗粒。
本发明的另一个主题是可以通过本发明的方法获得的聚酯。
本发明还涉及一种组合物,该组合物包含根据本发明的聚酯,该组合物可能还包含至少一种添加剂或至少一种另外的聚合物或至少一种其混合物。
根据本发明的聚酯组合物可以包含在该方法期间任选使用的聚合添加剂。其还可以包含总体上在随后的热机械混合步骤期间添加的其他添加剂和/或附加的聚合物。
通过添加剂的实例,可以提及有机或无机、纳米或非纳米的、官能化或非官能化性质的填充剂或纤维。它们可以是二氧化硅、沸石、玻璃纤维或珠、粘土、云母、钛酸盐、硅酸盐、石墨、碳酸钙、碳纳米管、木纤维、碳纤维、聚合物纤维、蛋白质、纤维素基纤维、木质纤维素纤维和非变性的颗粒淀粉。这些填充剂或纤维可以使得可能改进硬度、刚性或水渗透性或气体渗透性。相对于该组合物的总重量,该组合物可以包含按重量计从0.1%至75%(例如从0.5%至50%)的填充剂和/或纤维。具有在根据本发明的组合物中的用途的添加剂还可以包含遮光剂、染料和颜料。它们可以选自乙酸钴和以下化合物:HS-325Red BB(其是带有偶氮官能团的化合物,在名称Solvent Red 195下还被已知),HS-510Blue 2B(其是蒽醌)、Blue R、以及RSBViolet。
该组合物还可以包含作为添加剂的用于降低加工工具中的压力的加工助剂。还可以使用使得可以减小对用于形成该聚酯的材料(如模具或压延辊)的粘附的脱模助剂。这些助剂可以选自脂肪酸酯和脂肪酸酰胺、金属盐、皂、链烷烃和烃基蜡。这些助剂的具体实例是硬脂酸锌、硬脂酸钙、硬脂酸铝、硬脂酰胺、芥酸酰胺、山萮酸酰胺、蜂蜡或小烛树蜡。
根据本发明的组合物还可以包含其他添加剂,如稳定剂,例如光稳定剂、UV稳定剂和热稳定剂,流化剂,阻燃剂和抗静电剂。
该组合物还可以包含除根据本发明的聚酯之外的附加聚合物。该聚合物可以选自聚酰胺、除了根据本发明的聚酯之外的聚酯、聚苯乙烯、苯乙烯共聚物、苯乙烯-丙烯腈共聚物、苯乙烯-丙烯腈-丁二烯共聚物、聚(甲基丙烯酸甲酯)、丙烯酸共聚物、聚(醚-酰亚胺)、聚(苯醚)(如聚(2,6-二甲基苯醚))、聚(亚苯基硫酸酯)、聚(酯-碳酸酯)、聚碳酸酯、聚砜、聚砜醚、聚醚酮、以及这些聚合物的混合物。
该组合物还可以包含作为另外聚合物的使得可以改进聚合物的冲击特性的聚合物,尤其是官能化的聚烯烃如官能化的乙烯或丙烯聚合物和共聚物,核-壳共聚物或嵌段共聚物。
根据本发明的组合物还可以包含天然来源(如淀粉、纤维素、壳聚糖、藻酸盐、蛋白质(如谷蛋白、豌豆蛋白质、酪蛋白)、胶原、明胶或木质素)的聚合物,这些天然来源的聚合物可能是物理或化学地改性的。淀粉可以是以变性或增塑的形式使用。在后者情况下,增塑剂可以是水或多元醇,尤其是甘油、聚甘油、异山梨醇、脱水山梨糖醇、山梨醇、甘露醇或另外脲。文献WO 2010/010282 A1中描述的方法可以尤其用于制备该组合物。
根据本发明的组合物可以通过常规的热塑性混合方法来生产。这些常规方法包括至少一个混合处于熔融或软化状态的聚合物的步骤以及回收该组合物的步骤。该方法可以在桨式或转子式密炼机、外部混合机、或单螺杆或双螺杆同向旋转或反向旋转挤出机中进行。然而,优选的是通过挤出,特别是使用同向旋转挤出机生产该混合物。
该组合物的成分的混合可以在惰性气氛下进行。
在挤出机的情况下,可以借助于沿该挤出机定位的进料斗引入该组合物的各种成分。
本发明还涉及聚酯或组合物在光学制品领域(特别是用于制造光学透镜或光学膜)中的用途。它也可以用于制造多层制品。
本发明还涉及一种包含根据本发明的聚酯或组合物的塑料、成品或半成品。
该制品可以具有任何类型并且可以使用常规转化技术获得。
它可以是例如光学制品,即,要求良好光学特性的制品,如透镜、盘、透明或半透明的面板、发光二极管(LED)部件、光纤、用于LCD屏幕或另外窗的膜。由于根据本发明的聚酯的高玻璃化转变温度,光学制品具有能够靠近光源并且因此热源放置的优点,同时保持优异的尺寸稳定性和良好的耐光性。
根据本发明的制品还可以是多层制品,其至少一个层包括根据本发明的聚合物或组合物。这些制品可以在其中将以熔融状态的不同层的材料置于接触的情况下经由包括共挤出步骤的方法制造。通过举例,可以提及以下技术:管共挤出,型材共挤出,瓶子、小瓶或罐的共挤出吹塑模制(总体上被整理在术语“中空体的共挤出吹塑模制”下,)还被称为薄膜吹塑的共挤出吹塑模制,以及浇铸共挤出。
它们还可以根据如下方法来制造,该方法包括将熔融聚酯的层施加到处于固体状态的基于有机聚合物、金属或粘合剂组合物的层上的步骤。该步骤可以通过压制、通过包覆模制、成层或层压、挤出-层压、涂覆、挤出-涂覆或铺展来进行。
根据本发明的制品也可以是纤维、线或长丝。这些长丝可以通过各种方法获得,例如湿纺、干纺、熔纺、凝胶纺(或干-湿纺)或另外电纺丝。通过纺丝获得的长丝也可以被拉伸或定向。
如果需要,长丝可以被切成短纤维;这使得可以将这些纤维与其他纤维混合以产生混合物并获得线。
线或长丝也可以被织造,用于制造用于服装工业、地毯、窗帘、墙壁挂件、家用亚麻布、墙壁覆盖物、船帆、家具织物或者另外安全带或带子的织物。
这些线、纤维或长丝也可用作技术应用(例如管道、传动带、轮胎)中的增强剂,或作为任何其他聚合物基质中的增强剂。
这些线、纤维或长丝也可以以无纺布(例如毡)的形式、绳索的形式组装,或者另外以网的形式编织。
现在将在以下实例中说明本发明。要指明的是,这些实例不以任何方式限制本发明。
实例:
经由以下技术研究这些聚合物的特性:
通过差示扫描量热法(DSC)测量聚酯的热特性:首先将样品在氮气氛下在敞口的坩埚中从10℃加热至320℃(10℃.min-1),冷却至10℃(10℃.min-1),然后在与第一步骤相同的条件下再次加热至320℃。在第二次加热的中点处取玻璃化转变温度。任何结晶温度在冷却时的放热峰(起始)上确定。在第二次加热时在吸热峰(起始)上确定任何熔点。类似地,在第二次加热时确定熔化焓(曲线下面积)。
使用Ubbelohde毛细管粘度计在35℃下评估溶液中比浓粘度。在磁力搅拌下,在130℃下,将聚合物预先溶解在邻氯苯酚中。对于这些测量而言,引入的聚合物浓度是5g/l。最终聚酯的异山梨醇的含量通过1H NMR通过对关于该聚酯的每种单元的信号进行积分确定。
对于以下呈现的说明性实例,使用以下试剂:
-来自西格玛-奥德里奇公司(Sigma-Aldrich)的乙二醇(纯度>99.8%)
-来自TCI公司的螺环二醇(纯度>97%)
-来自西格玛-奥德里奇公司(Sigma-Aldrich)的三环[5.2.1.02,6]癸烷二甲醇(TCDDM,纯度96%)
-异山梨醇(纯度>99.5%),来自法国罗盖特公司(Roquette Frères)的P
-来自阿克罗斯公司(Acros)的对苯二甲酸(99+%纯度)
-2,5-呋喃二甲酸(纯度99.7%),来自Satachem公司
-来自西格玛-奥德里奇公司的间苯二甲酸(纯度99%)
-2,6-萘二甲酸(纯度99.8%),来自巴斯夫公司(BASF)
-来自西格玛-奥德里奇公司的二氧化锗(>99.99%)
-来自西格玛-奥德里奇公司的二氧化二丁基锡(纯度98%)
聚酯的制备:
实例1:
将25g的对苯二甲酸二甲酯、2.4g的异山梨醇、67.5g的螺环二醇和20mg的二氧化二丁基锡引入反应器中。通过150rpm的机械搅拌搅拌该混合物,并在氮气流下在15min的过程中将其加热至190℃。仍然在氮气流和机械搅拌下,然后将反应介质在190℃下保持5分钟,然后在10分钟的过程中再次加热至265℃。将这个温度保持3h。
在此之后,将温度升高至300℃,压力在1小时的过程中降低至0.7毫巴,并将搅拌速度降低至50rpm。这些条件将被保持3h。
获得的聚合物是半结晶材料,其玻璃化转变温度为130℃,具有200℃的结晶温度,281℃的熔点以及63.8ml/g的比浓粘度(在35℃下在2-氯苯酚中5g/l的浓度)。通过NMR对最终聚酯的分析示出5%的异山梨醇(相对于二醇)已经被引入到聚合物链中。
实例1a:
将来自实例1的聚酯用于固态后缩合步骤。首先,将聚合物在190℃下在真空下在烘箱中结晶2小时。然后将结晶的聚合物引入装有空心烧瓶的油浴旋转蒸发器中。然后使颗粒经受270℃的温度和3.3l/min的氮气流量。在后缩合25小时后,聚合物将具有105.8ml/g的溶液中比浓粘度。
实例2:
将25g的对苯二甲酸二甲酯、10.5g的异山梨醇、50.8g的螺环二醇和20mg的二氧化二丁基锡引入反应器中。通过150rpm的机械搅拌搅拌该混合物,并在氮气流下在15min的过程中将其加热至190℃。仍然在氮气流和机械搅拌下,然后将反应介质在190℃下保持5分钟,然后在10分钟的过程中再次加热至265℃。将这个温度保持4h。
在此之后,将温度升高至300℃,压力在1小时的过程中降低至0.7毫巴,并将搅拌速度降低至50rpm。这些条件将被保持4h。
获得的聚合物是无定形材料,其玻璃化转变温度为149℃并且其比浓粘度为54.9ml/g(在35℃下在2-氯苯酚中5g/l的浓度)。通过NMR对最终聚酯的分析示出27%的异山梨醇(相对于二醇)已经被引入到聚合物链中。
实例3:
将25g的2,6-萘二甲酸、4.0g的异山梨醇、33.3g的螺环二醇和20mg的二氧化二丁基锡引入反应器中。通过150rpm的机械搅拌搅拌该混合物,并在氮气流下在15min的过程中将其加热至230℃。仍然在氮气流和机械搅拌下,然后将反应介质在230℃下保持5分钟,然后在10分钟的过程中再次加热至265℃。将这个温度保持4h。
在此之后,将温度升高至310℃,压力在1小时的过程中降低至0.7毫巴,并将搅拌速度降低至50rpm。这些条件将被保持4h。
获得的聚合物是半结晶材料,其玻璃化转变温度为169℃,具有210℃的结晶温度,292℃的熔点以及49.4ml/g的比浓粘度(在35℃下在2-氯苯酚中5g/l的浓度)。通过NMR对最终聚酯的分析示出17%的异山梨醇(相对于二醇)已经被引入到聚合物链中。
实例3a:
将来自实例3的聚酯用于固态后缩合步骤。首先,将聚合物在190℃下在真空下在烘箱中结晶2小时。然后将结晶的聚合物引入装有空心烧瓶的油浴旋转蒸发器中。然后使颗粒经受270℃的温度和3.3l/min的氮气流量。在后缩合28小时后,聚合物将具有78.2ml/g的溶液中比浓粘度。
实例4:
将25g的对苯二甲酸二甲酯、42.2g的4,8-三环[5.2.1.02,6]癸烷二甲醇(异构体的混合物)、4.2g的异山梨醇和17.9mg的氧化二丁基锡引入反应器中。通过150rpm的机械搅拌搅拌该混合物,并在氮气流下在10min的过程中将其加热至190℃。仍然在氮气流和机械搅拌下,然后将反应介质在190℃下保持5分钟,然后在20分钟的过程中再次加热至250℃。将这个温度保持120分钟。
在此之后,将温度升高至280℃,压力在30min的过程中降低至0.7毫巴,并将搅拌速度降低至50rpm。这些条件将被保持3h。
获得的聚合物是无定形材料,其玻璃化转变温度为119℃并且其比浓粘度为58.4ml/g(在35℃下在2-氯苯酚中5g/l的浓度)。通过NMR对最终聚酯的分析示出11%的异山梨醇(相对于二醇)已经被引入到聚合物链中。
实例5:
将25g的对苯二甲酸二甲酯、33.5g的4,8-三环[5.2.1.02,6]癸烷二甲醇(异构体的混合物)、10.7g的异山梨醇和17.9mg的氧化二丁基锡引入反应器中。通过150rpm的机械搅拌搅拌该混合物,并在氮气流下在10min的过程中将其加热至190℃。仍然在氮气流和机械搅拌下,然后将反应介质在190℃下保持5分钟,然后在20分钟的过程中再次加热至250℃。将这个温度保持180分钟。
在此之后,将温度升高至280℃,压力在30min的过程中降低至0.7毫巴,并将搅拌速度降低至50rpm。这些条件将被保持4小时30分钟。
获得的聚合物是无定形材料,其玻璃化转变温度为135℃并且其比浓粘度为51.3ml/g(在35℃下在2-氯苯酚中5g/l的浓度)。通过NMR对最终聚酯的分析示出27%的异山梨醇(相对于二醇)已经被引入到聚合物链中。
Claims (14)
1.一种热塑性聚酯,包含:
-至少一种1,4:3,6-双脱水己糖醇单元(A);
-至少一种除了环己烷二甲醇单元和所述1,4:3,6-双脱水己糖醇单元(A)以外的环状二醇单元(B);
-至少一种芳香族二羧酸单元(C);
所述聚酯不含乙二醇单元。
2.如权利要求1所述的聚酯,具有至少95℃、优选至少100℃、更优先至少110℃并且更优先还至少120℃的玻璃化转变温度。
3.如前述权利要求中任一项所述的聚酯,其中该1,4:3,6-双脱水己糖醇(A)是异山梨醇。
4.如权利要求1和2中任一项所述的聚酯,其中该环状二醇(B)选自螺环二醇、三环[5.2.1.02,6]癸烷二甲醇(TCDDM)、2,2,4,4-四甲基-1,3-环丁二醇、四氢呋喃二甲醇(THFDM)、呋喃-二甲醇、1,2-环戊二醇、1,3-环戊二醇、1,2-环己二醇、1,4-环己二醇、1,2-环庚二醇、1,5-萘二酚、2,7-萘二酚、1,4-萘二酚、2,3-萘二酚、2-甲基-1,4-萘二酚、1,4-苯二酚、八氢萘-4,8-二醇、二噁烷二醇(DOG)、降冰片烷二醇、金刚烷二醇和五环十五烷二甲醇。
5.如前述权利要求之一所述的聚酯,其特征在于该聚酯不含环己烷二甲醇单元。
6.如前述权利要求中任一项所述的聚酯,其中该聚酯包含:
-在从5%至45%范围内的摩尔量的1,4:3,6-双脱水己糖醇单元(A);
-在从3%至47%范围内的摩尔量的除了环己烷二甲醇单元和所述1,4:3,6-双脱水己糖醇单元(A)以外的环状二醇单元(B);
-在从48%至52%范围内的摩尔量的二羧酸单元(C)。
7.如前述权利要求之一所述的聚酯,其特征在于该聚酯是无定形的。
8.如权利要求1至6之一所述的聚酯,其特征在于该聚酯是半结晶的。
9.一种用于生产如前述权利要求之一所述的聚酯的方法,所述方法包括:
-将单体引入反应器的步骤,所述单体包含至少一种1,4:3,6-双脱水己糖醇(A),至少一种除了所述1,4:3,6-双脱水己糖醇(A)以外的脂环族二醇(B)和至少一种二羧酸(C),所述单体不含乙二醇;
-将催化体系引入该反应器中的步骤;
-聚合所述单体以形成该聚酯的步骤,所述步骤由以下各项组成:
■低聚的第一阶段,在该第一阶段期间,首先将反应介质在惰性气氛下在范围从150℃至250℃、有利地从170℃至240℃、更有利地从180℃至235℃的温度下进行搅拌,然后使其达到范围从230℃至300℃、有利地范围从240℃至290℃、更有利地从245℃至270℃的温度;
■低聚物缩合的第二阶段,在该第二阶段期间,在真空下在范围从240℃至320℃、有利地从275℃至310℃、更有利地从289℃至310℃的温度下搅拌所形成的低聚物以便形成该聚酯;以及
-回收该聚酯的步骤。
10.如权利要求9所述的方法,其中该聚酯是半结晶的,并且该方法包括以下步骤:在真空下或在用惰性气体冲洗时并且在比该聚酯的熔点低5℃至30℃的温度下进行固态后缩合。
11.一种能够通过如权利要求9或10所述的方法获得的聚酯。
12.一种聚酯组合物,包含如权利要求1至8或11之一所述的聚酯。
13.如权利要求1至8或11之一所述的聚酯或如权利要求12所述的组合物在光学制品或多层塑料制品领域中的用途。
14.一种塑料制品,包含如权利要求1至8或11之一所述的聚酯或如权利要求12所述的组合物。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1561753 | 2015-12-02 | ||
FR1561753A FR3044665A1 (fr) | 2015-12-02 | 2015-12-02 | Copolyesters thermoplastiques aromatiques comprenant du 1,4 : 3,6-dianhydrohexitol et divers diols cycliques |
FR1651205A FR3044667B1 (fr) | 2015-12-02 | 2016-02-15 | Copolyesters thermoplastiques aromatiques comprenant du 1,4 : 3,6-dianhydrohexitol et divers diols cycliques |
FR1651205 | 2016-02-15 | ||
PCT/FR2016/053180 WO2017093685A1 (fr) | 2015-12-02 | 2016-12-02 | Copolyesters thermoplastiques aromatiques comprenant du 1,4 : 3,6-dianhydrohexitol et divers diols cycliques |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108431078A true CN108431078A (zh) | 2018-08-21 |
CN108431078B CN108431078B (zh) | 2021-08-06 |
Family
ID=55650570
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201680070741.4A Active CN108431078B (zh) | 2015-12-02 | 2016-12-02 | 含1,4:3,6-双脱水己糖醇和各种环状二醇的芳香族热塑性共聚酯 |
Country Status (9)
Country | Link |
---|---|
US (1) | US20180362707A1 (zh) |
EP (1) | EP3383932A1 (zh) |
JP (1) | JP2018536073A (zh) |
KR (1) | KR20180089418A (zh) |
CN (1) | CN108431078B (zh) |
CA (1) | CA3006905A1 (zh) |
FR (2) | FR3044665A1 (zh) |
MX (1) | MX2018006685A (zh) |
WO (1) | WO2017093685A1 (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111072940A (zh) * | 2019-11-28 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | 基于螺环乙二醇的共聚酯及其制备方法、制品 |
CN111303394A (zh) * | 2020-04-20 | 2020-06-19 | 河南功能高分子膜材料创新中心有限公司 | 一种改性耐高温聚酯的制备方法及改性耐高温聚酯 |
CN111471167A (zh) * | 2020-05-12 | 2020-07-31 | 河南功能高分子膜材料创新中心有限公司 | 一种改性耐高温抗水解共聚聚酯 |
CN116135904A (zh) * | 2021-11-16 | 2023-05-19 | 南亚塑胶工业股份有限公司 | 聚合物树脂及其制造方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102670942B1 (ko) * | 2016-02-04 | 2024-05-31 | 에스케이케미칼 주식회사 | 내열성 및 용제 용해성이 우수한 폴리에스테르 수지 및 이를 함유하는 코팅 조성물 |
FR3065958B1 (fr) * | 2017-05-05 | 2020-09-04 | Roquette Freres | Procede de fabrication d'un materiau composite |
CH715228A1 (de) * | 2018-08-02 | 2020-02-14 | Alpla Werke Alwin Lehner Gmbh & Co Kg | Preform aus Polyester. |
KR102478598B1 (ko) * | 2019-08-30 | 2022-12-15 | 코오롱인더스트리 주식회사 | 바이오매스 유래 환형 단량체를 포함하는 고분자 화합물 및 그의 제조방법 |
FR3105232B1 (fr) | 2019-12-20 | 2021-12-24 | Roquette Freres | Procédé de fabrication d’un polyester contenant au moins un motif 1,4 : 3,6-dianhydrohexitol à coloration réduite et taux d’incorporation dudit motif améliorés |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1322671A (fr) * | 1961-05-26 | 1963-03-29 | Atlas Chem Ind | Résines de polyesters perfectionnées et leur procédé de préparation |
CN1252078A (zh) * | 1997-02-06 | 2000-05-03 | Basf公司 | 手性向列型聚酯 |
CN1298343A (zh) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | 含异山梨醇的聚酯及其制备方法 |
CN101111545A (zh) * | 2005-02-02 | 2008-01-23 | 三菱瓦斯化学株式会社 | 聚酯薄膜及其制备方法以及其用途 |
CN103298851A (zh) * | 2010-12-10 | 2013-09-11 | 三菱瓦斯化学株式会社 | 聚酯树脂以及光学透镜 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19756974C2 (de) * | 1997-12-20 | 2001-04-19 | Clariant Gmbh | Organisches Material mit metallischem Glanz |
KR101775620B1 (ko) * | 2011-04-06 | 2017-09-07 | 에스케이케미칼주식회사 | 코팅용 폴리에스테르 바인더 수지 및 이를 함유하는 코팅 조성물 |
US20130095270A1 (en) * | 2011-10-14 | 2013-04-18 | Eastman Chemical Company | Polyester compositions containing furandicarboxylic acid or an ester thereof, cyclobutanediol and cyclohexanedimethanol |
EP2935394A2 (en) * | 2012-12-20 | 2015-10-28 | Dow Global Technologies LLC | Fdca-based polyesters made with isosorbide |
FR3020811B1 (fr) * | 2014-05-09 | 2016-06-10 | Roquette Freres | Polyesters aromatiques thermoplastiques comprenant des motifs tetrahydrofuranedimethanol et acide furanedicarboxylique |
-
2015
- 2015-12-02 FR FR1561753A patent/FR3044665A1/fr active Pending
-
2016
- 2016-02-15 FR FR1651205A patent/FR3044667B1/fr active Active
- 2016-12-02 WO PCT/FR2016/053180 patent/WO2017093685A1/fr active Application Filing
- 2016-12-02 US US15/781,387 patent/US20180362707A1/en not_active Abandoned
- 2016-12-02 EP EP16819348.0A patent/EP3383932A1/fr active Pending
- 2016-12-02 KR KR1020187015250A patent/KR20180089418A/ko not_active Application Discontinuation
- 2016-12-02 CN CN201680070741.4A patent/CN108431078B/zh active Active
- 2016-12-02 CA CA3006905A patent/CA3006905A1/fr not_active Abandoned
- 2016-12-02 JP JP2018528647A patent/JP2018536073A/ja active Pending
- 2016-12-02 MX MX2018006685A patent/MX2018006685A/es unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1322671A (fr) * | 1961-05-26 | 1963-03-29 | Atlas Chem Ind | Résines de polyesters perfectionnées et leur procédé de préparation |
CN1252078A (zh) * | 1997-02-06 | 2000-05-03 | Basf公司 | 手性向列型聚酯 |
CN1298343A (zh) * | 1998-04-23 | 2001-06-06 | 纳幕尔杜邦公司 | 含异山梨醇的聚酯及其制备方法 |
CN101111545A (zh) * | 2005-02-02 | 2008-01-23 | 三菱瓦斯化学株式会社 | 聚酯薄膜及其制备方法以及其用途 |
CN103298851A (zh) * | 2010-12-10 | 2013-09-11 | 三菱瓦斯化学株式会社 | 聚酯树脂以及光学透镜 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111072940A (zh) * | 2019-11-28 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | 基于螺环乙二醇的共聚酯及其制备方法、制品 |
CN111072940B (zh) * | 2019-11-28 | 2021-09-28 | 中国科学院宁波材料技术与工程研究所 | 基于螺环乙二醇的共聚酯及其制备方法、制品 |
CN111303394A (zh) * | 2020-04-20 | 2020-06-19 | 河南功能高分子膜材料创新中心有限公司 | 一种改性耐高温聚酯的制备方法及改性耐高温聚酯 |
CN111471167A (zh) * | 2020-05-12 | 2020-07-31 | 河南功能高分子膜材料创新中心有限公司 | 一种改性耐高温抗水解共聚聚酯 |
CN111471167B (zh) * | 2020-05-12 | 2022-08-09 | 河南功能高分子膜材料创新中心有限公司 | 一种改性耐高温抗水解共聚聚酯 |
CN116135904A (zh) * | 2021-11-16 | 2023-05-19 | 南亚塑胶工业股份有限公司 | 聚合物树脂及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
FR3044667B1 (fr) | 2020-02-14 |
WO2017093685A1 (fr) | 2017-06-08 |
FR3044667A1 (fr) | 2017-06-09 |
CA3006905A1 (fr) | 2017-06-08 |
FR3044665A1 (fr) | 2017-06-09 |
JP2018536073A (ja) | 2018-12-06 |
EP3383932A1 (fr) | 2018-10-10 |
US20180362707A1 (en) | 2018-12-20 |
CN108431078B (zh) | 2021-08-06 |
MX2018006685A (es) | 2018-08-24 |
KR20180089418A (ko) | 2018-08-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108431078A (zh) | 含1,4:3,6-双脱水己糖醇和各种环状二醇的芳香族热塑性共聚酯 | |
JP6937247B2 (ja) | 衝撃特性が改善された高粘度ポリマー | |
CN101018824B (zh) | 树脂组合物及其成型体 | |
JP6688792B2 (ja) | 改良された着色を有する、少なくとも1つの1,4:3,6−ジアンヒドロヘキシトール単位を含有するポリエステルを生成する方法 | |
CN108368242A (zh) | 含1,4:3,6-双脱水己糖醇和各种芳香族二酸的热塑性共聚酯 | |
TWI845475B (zh) | 聚酯纖維、製備聚酯纖維的方法以及以聚酯纖維製成之樹脂模製品 | |
JP7014771B2 (ja) | 3d印刷物を製造するための熱可塑性ポリエステル | |
JP7320499B2 (ja) | 1,4:3,6-ジアンヒドロ-l-イジトール単位の高い取込み度を有する熱可塑性ポリエステル | |
JP2019523321A (ja) | 繊維を製造するための半結晶性熱可塑性ポリエステル | |
JP7133541B2 (ja) | 光学物品の製造のための非晶質熱可塑性ポリエステル | |
US20220002476A1 (en) | Method for preparing a polyester of the poly(1,4:3,6-dianhydrohexitol-cocyclohexylene terephthalate) type | |
JP2023506882A (ja) | 少なくとも1つの1,4:3,6-ジアンヒドロヘキシトールユニットを含有するポリエステルの、着色が低減され該ユニット組み込み率が改善された製造方法 | |
JP2023532477A (ja) | 3dプリントされた物体製造用の熱可塑性ポリエステル |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |