CN104371310A - Improved elastomer composition - Google Patents
Improved elastomer composition Download PDFInfo
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- CN104371310A CN104371310A CN201410612755.7A CN201410612755A CN104371310A CN 104371310 A CN104371310 A CN 104371310A CN 201410612755 A CN201410612755 A CN 201410612755A CN 104371310 A CN104371310 A CN 104371310A
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Abstract
The invention relates to a novel polyurethane, copolyether ester or copolyether amide elastomer composition. The composition comprises diol which is prepared by performing random copolymerization on alkylene oxide and tetrahydrofuran (THF), namely, poly(tetramethylene-co-alkylene ether) diol, wherein alkylene oxide comprises 2 to 4 carbon atoms.
Description
The application is PCT international filing date is on December 11st, 2009, and the denomination of invention that PCT international application no is PCT/US2009/067680, China national application number is 200980162853.2 is the divisional application of the application of " elastic composition of improvement ".
Background of invention
The present invention relates to novel elastic composition and with their produce structure and product.Described structure and product, such as, film, film or coating, be the hypertonicity material with good physical strength, which overcome the shortcoming of prior art.These materials'use random copolymerization ethoxylated polyhydric alcohol soft chain segments, described soft chain segment has the oxirane of about 20 to about 75 % by mole, such as oxyethane (EO) content, and can easily form film, film or coating.These elastic compositions can be urethane, copolyether ester or copolyether amide.The random copolyether polyol soft segment of described elastic composition comprises the glycol obtained by oxirane and tetrahydrofuran (THF) (THF) random copolymerization, i.e. poly-(tetramethylene-co-alkylene ether) glycol, described oxirane has 2 to 4 carbon atoms.
It is known that the wetting ability of described polymkeric substance will be improved containing ethylene oxide unit in the polymer, and affect the water vapour permeability of the goods be made up of this polymkeric substance.Due to this character at the waterproof cloth goods of particular product such as ventilation property and pharmaceutical products as the importance in bandage and wound dressings, investigators have attempted affecting these character by multiple different methods.These class methods many and the goods containing described material have bothersome shortcoming or deficiency, this generates and such as increase production cost or provide not enough Water Transportation degree, or mechanical property is as the problem of tensile strength.
U.S. Patent number 6,133,400 instructions, can prepare the reactive hot-melt binder formulation that vapor permeation speed (MVTR) is greater than 100 grams-mil/square metre-day, and it comprises by oxyethane, propylene oxide or butylene oxide ring or the derivative polyether glycol of its combination.The polyester polyol of these materials and crystalline state, other polyether glycol and polymeric polyisocyanate are combined, to obtain described tackiness agent.These materials provide certain Water Transportation degree, but the existence depending on moisture forms necessary amine to generate for chain extension and hard segment.A kind of addition reaction product is carbonic acid gas, and it can cause physical imperfection.In addition, in order to the effect by ambient moisture is solidified completely, described tackiness agent needs the storage extended, and described method must be carried out usually in certain support materials.
U.S. Patent number 5,908,690 describe waterproof by extruded thermoplastic polyurethane production and air-permeating film, and described thermoplastic polyurethane contains 35 to 60 % by weight soft chain segments be made up as ethylene oxide polymer and multipolymer etc. of polyethylene oxide or polyethylene oxide reaction product.THF be provided as can with the example of the cyclic ethers of oxyethane copolymerization.Product described in this publication depends on a large amount of ethylene oxide unit (form of polyoxyethylene glycol soft chain segment) to obtain the perviousness of expection.Do not provide any soft chain segment example being different from polyoxyethylene glycol, and described amount is by weight higher than 42 % by weight.Usually, the goods produced by polyoxyethylene glycol lack enough physical strengths, and may cause moisture absorption too high in the final product.In addition, in order to obtain the performance of expecting, need to use toughener (silicon-dioxide) and chain terminator.
EP 0620506 A2 discloses a kind of reinforced element used in photocopy, and described reinforced element utilizes the moisture permeable synthetic resins as upper layer to be formed.A kind of form of described synthetic resins is the urethane resin with soft chain segment, described soft chain segment is made up of the random copolymers of oxyethane and tetrahydrofuran (THF), the molar ratio of the EO/THF of described random copolymers is 40/60 to 80/20, and molecular weight is 600 to 3000.Product described in this publication is produced with unspecified soft segment concentration by mass polymerization or solution polymerization.Described material must be melt-processable, and in order to effective, is granulated further, dissolves in a solvent and be coated on elastomeric material.Although perviousness and swelling ratio have been quoted as the key request of effectiveness, composition required for protection is not provided to the numerical value of these performances.
U.S. Patent number 5,035,893 disclose a kind of wound dressings be made up of biopolymer materials and moisture permeable film.The urethane resin of this material is made up of vulcabond, chainextender and tetrahydrofuran (THF)-ethylene oxide copolymer polyvalent alcohol in the solution.Described polyvalent alcohol contains the oxyethane of 20 to 80 % by weight, and has 800 to 3000 daltonian molecular weight.Product described in this publication is confined to: prepare diamines expansion polymkeric substance in the solution.In order to be prepared into the film on biopolymerization base material, described product has to pass through precipitation and dissolves in acceptable solvent again.
EP 0974696 A1 describes a kind of joint seal composition for moisture permeable goods.Described composition is a kind of solution containing copolyether ester (COPE) applied on goods, and in described copolyether ester, the carbon/oxygen ratio of soft chain segment is 2.0 to 4.3 and molecular weight is 600 to 4000 dalton.Described sealing compositions is the blend of polyoxyethylene glycol (PEG) and polytetramethylene ether diol (PTMEG), and in order to be created on the copolyesters of the low melt in halocarbon solvent with sufficient solubleness, by adding aliphatic series or the further modification of asymmetric aromatic diacid.Necessary swelling in order to obtain for adhering to, need to use halocarbon solvent.Use the shortcoming of homopolymer PEG, namely poor mechanical property and excessive water-absorbent, expect.
EP 0622488 B1 describes a kind of waterproof article, wherein COPE pellicular cascade is formed fabric, and described film is prepared described in EP 0974696 A1, but does not use solvent and by hot pressing film.Product described in this publication comprises the mixture of naphthalic acid and BDO (4GN) hard segment and polyoxyethylene glycol soft chain segment or polyoxyethylene glycol and polytetramethylene ether diol.
U.S. Patent number 4,937,314 disclose the thermoplastic copolyether ester elastomer containing the soft chain segment that at least 70 % by weight are derived by poly-(oxirane) glycol and terephthalic acid.Hard segment accounts for described elastomeric 10 to 30 % by weight, and is poly-(the terephthalic acid 1,3-PD ester) of 95 to 100%.The specification disclosing poly-(oxirane) glycol has from 1,500 to 5, the molecular weight of 000, and the carbon of 2 to 4.3/oxygen ratio.Representational poly-(oxirane) glycol comprises poly-(oxyethane) glycol, poly-(1,2 epoxy prapane) glycol, poly-(1，3-epoxypropane) glycol, poly-(butylene oxide ring) glycol etc.In the illustration being described, soft chain segment is based on PTMEG and tetrahydrofuran (THF)/oxyethane copolyether.
U.S. Patent number 5,128,185 describe the thermoplastic copolyether ester elastomer containing the soft chain segment that at least 83 % by weight are derived by poly-(oxirane) glycol and terephthalic acid.Hard segment accounts for 10-17 % by weight and comprises poly-(diphenic acid 1,3-PD ester).The specification disclosing poly-(oxirane) glycol has from 1,500 to 5, the molecular weight of 000, and the carbon of 2.5 to 4.3/oxygen ratio.Representational example comprises poly-(oxyethane) glycol, poly-(1,2 epoxy prapane) glycol, poly-(1，3-epoxypropane) glycol, poly-(butylene oxide ring) glycol etc.In the illustration being described, soft chain segment is based on PTMEG and tetrahydrofuran (THF)/3-methyltetrahydrofuran.
Technology described in above-mentioned publication and composition are confined to: they use polyoxyethylene glycol or its mixture, and other polyvalent alcohol is as poly-(1,2-propylene oxide) glycol (PPG) or ethylene oxide-capped polypropylene glycol (EOPPG), instead of use the oxirane of such as oxyethane and the random copolymers of THF.Generally acknowledge that mechanical property is poor by the derivative thermoplastic polyurethane of PPG or EOPPG or copolyether ester with compared with the obtained thermoplastic polyurethane of polytetramethylene ether diol (PTMEG) or copolyether ester.When describing oxirane and THF and be polymerized glycol (the EOTHF random copolymers) that obtain, they need to use ancillary component, and described material by solution coated with generating permeable film.Do not instruct in these publications or imply following elastic composition, described elastic composition comprises: from about 20 to less than about 70 % by weight, such as 69 % by weight, first component polyvalent alcohol, described first component polyvalent alcohol is obtained by the random copolymerization of the oxirane and tetrahydrofuran (THF) with 2 to 4 carbon atoms, such as poly-(tetramethylene-co-alkylene ether) glycol; With from more than about 30, such as 31 % by weight to 80 % by weight second component urethane, copolyether ester or copolyether amide, described elastic composition has the steam permeating rate being greater than about 250 grams-mil/square metre-day, and > is about the tensile strength of 1500psi.These novel elastomer composites have in this as the unique combination of character disclosed in limiting examples as moisture permeable and physical strength.
Summary of the invention
Therefore, the structure desirably providing the novel elastic composition with suitable character and produce with their and product, described character comprises the steam permeating rate being greater than about 250 grams-mil/square metre-day, particularly from about 500 to about 2000 grams-mil/square metre-day, and good physical strength, such as, according to ASTM D412, tensile strength > 1500psi.
Structure of the present invention and product, such as film are the hypertonicity materials with good mechanical strength, which overcome the shortcoming that similar structures body and product in the prior art run into.These materials'use random copolymerization ethoxylated polyhydric alcohol soft chain segments, described soft chain segment has the oxirane of from about 20 to about 75 % by mole, the content of such as oxyethane, and can easily form film.These elastic compositions can be urethane, copolyether ester or copolyether amide.The random copolymerization ethoxylated polyhydric alcohol soft chain segment of described elastic composition comprises the glycol obtained by oxirane and tetrahydrofuran (THF) (THF) random copolymerization, i.e. poly-(tetramethylene-co-alkylene ether) glycol, described oxirane has 2 to 4 carbon atoms.Novel elastomer composites of the present invention is very useful in such as fiber and thin film industry.When being used as film, such as fabric laminated to prepare breathable cloth time, novel elastomer composites of the present invention has the flexility of excellent balance, stretching and tear resistance and resistant to hydrolysis performance.Another advantage of this type of novel elastomer composites can be more economic to manufacture the moisture controlled product with special performance.
Therefore, important embodiment of the present invention provides new polyurethane, copolyether ester or copolyether amide elastic composition, described composition contains the glycol obtained by oxirane and tetrahydrofuran (THF) (THF) random copolymerization, i.e. poly-(tetramethylene-co-alkylene ether) glycol, described oxirane has 2 to 4 carbon atoms.Elastic composition of the present invention has the unique combination of following character, and described character comprises: tractability and reactivity; And be greater than the steam permeating rate, particularly from about 500 to about 2000 grams-mil of about 250 grams-mil/square metre-day/square metre-day; And good physical strength, such as, according to ASTM D412, tensile strength > 1500psi; And be greater than the percentage elongation of about 200%, particularly from about 300 to about 900%.
More particularly, important embodiment of the present invention provides novel urethane or copolyether ester or copolyether amide elastic composition, described composition comprises the glycol obtained by the random copolymerization of oxyethane and tetrahydrofuran (THF) (THF), namely poly-(tetramethylene-co-ethyleneether) glycol.
Further, important embodiment of the present invention is a kind of structure or product, it comprises novel urethane or copolyether ester or copolyether amide elastic composition, described composition comprises the glycol obtained by the random copolymerization of oxirane and tetrahydrofuran (THF) (THF), i.e. poly-(tetramethylene-co-alkylene ether) glycol, described oxirane has 2 to 4 carbon atoms.The structure or the product that comprise this elastic composition of the present invention can be such as film or coating.
Describe in detail
The invention discloses a kind of method of producing novel urethane, copolyether ester or copolyether amide elastic composition, described composition comprises the glycol obtained by the random copolymerization of oxirane and tetrahydrofuran (THF) (THF), i.e. poly-(tetramethylene-co-alkylene ether) glycol, described oxirane has 2 to 4 carbon atoms, to obtain certain expected performance.Described poly-(tetramethylene-co-alkylene ether) glycol can according to being combined in this U.S. Patent number 4,139 by reference, the method manufacture described in 567, or by hereinafter described method manufacture.
As use alpha nerein, term " polymer " " refer to the product of polyreaction, it comprises homopolymer, multipolymer, terpolymer etc.
As use alpha nerein, unless otherwise mentioned, term " multipolymer " refers to the polymkeric substance formed by least two kinds of monomer polymerizations.Such as, term " multipolymer " comprises ethene and alpha-olefm (alpha-olefin), such as propylene as an example and 1-hexene, or oxirane is as the copolyreaction product of oxyethane and tetrahydrofuran (THF).But, term " multipolymer " also comprises, such as, and the copolymerization of the mixture of ethene, propylene, 1-hexene and 1-octene or the mixture of multiple aklylene glycol and tetrahydrofuran (THF).
As use alpha nerein, unless separately glossed, molar percentage (" % by mole ") refers to that concrete component is based on the per-cent of total mole number of mixture comprising this component.Such as, if mixture comprises a three molar constituent A and molar constituent B, then component A accounts for 75 % by mole of mixture and B component accounts for 25 % by mole.This theory is also for the title of weight percent (" % by weight ").
Urethane of the present invention or copolyether ester or copolyether amide elastic composition contain from 20 to the first component glycol less than about 70 % by weight such as 69 % by weight, preferably from about 35 to about 65 % by weight, i.e. soft chain segment, described glycol is obtained by the random copolymerization of oxirane and tetrahydrofuran (THF) (THF), described oxirane has 2 to 4 carbon atoms, such as oxyethane (EO), propylene oxide or butylene oxide ring.Described composition also comprises and accounts for more than the second component urethane of about 30 % by weight such as 31 % by weight to about 80 % by weight, preferably from about 35 to about 65 % by weight, copolyether ester or copolyether amide, i.e. hard segment.Described composition exhibiting goes out estimated performance, described estimated performance comprises and is greater than about 250 grams-mil/square metre-day, the steam permeating rate of particularly from about 500 to about 2000 grams-mil/square metre-day, and good physical strength, such as, according to ASTM D412, tensile strength > 1500psi.
The oxirane needed to use at this and the random copolymers of tetrahydrofuran (THF), namely poly-(tetramethylene-co-alkylene ether) glycol, is prepared by the positively charged ion ring opening copolymer of oxirane and tetrahydrofuran (THF).Final polyvalent alcohol has from about 500 to about 3000 daltonian molecular weight, and has the oxirane combination rate of from about 20 to about 75 % by mole.
Comprise the steps: that oxirane that tetrahydrofuran (THF) and at least one to have 2 to 4 carbon atoms by (a) to contain at acid catalyst and at least one under the existence of the compound of hydrogen atoms in the temperature polymerizations of about 50 DEG C to about 80 DEG C for the preparation of the process useful of described poly-(tetramethylene-co-alkylene ether) glycol, to prepare polymer product mixture, it comprises oligomeric cyclic ethers, copolyether glycol, at least one oxirane dipolymer and tetrahydrofuran (THF); (b) from the polymer product mixture of step (a) separating most tetrahydrofuran (THF) and oxirane dipolymer at least partially, to prepare the crude product mixture containing oligomeric cyclic ethers and copolyether glycol; And (c) from the crude product mixture of step (b) in separating oligomeric cyclic ethers at least partially, to generate oligomeric cyclic ethers stream containing oligomeric cyclic ethers and the product stream containing poly-(tetramethylene-co-alkylene ether) glycol.
In this process useful, described oxirane is selected from: oxyethane; 1,2 epoxy prapane; 1，3-epoxypropane; 1,2-butylene oxide ring; 2,3-butylene oxide ring; 1,3-butylene oxide ring and their combination.The described compound containing hydrogen atoms is selected from: water; Ethylene glycol; BDO; Molecular weight is that about 130 dalton are to about 400 daltonian polytetramethylene ether diols; Molecular weight is that about 130 dalton are to about 400 daltonian copolyether glycol; And their combination.Described acid catalyst is selected from: the compound of the natural or synthetic zeolite of acidifying natural clay, acidifying, sheet silicate optionally by acid treatment activation, acidifying zirconium/tin sulphate cpd, the coating oxygen containing molybdenum containing at least one catalytic activity on an oxidic support and/or tungsten part, containing sulfonic polyalcohol catalyst and their combination.Described tetrahydrofuran (THF) component can contain at least one alkyl tetrahydro furans, and it is selected from: 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran and their combination.
Novel elastomer composites of the present invention and containing the blend of said composition or mixture, can also stabilizer additive containing significant quantity or compound, such as, in order to prevent from forming color.Many such stablizers (such as, antioxidant, UV light stabilizing agent and thermo-stabilizer) are well known in the art, and wherein any one all can use with compatible products disclosed herein jointly.In stablizer, the benzophenone of replacement, phenolic compound, carbon black and sulphur compound can be used for the present invention.
Novel elastomer composites of the present invention and containing the blend of said composition or mixture, can also tinting pigment additive containing significant quantity or compound.Many tinting pigments for product of the present invention and the mixture containing described product are well known in the art, and wherein any one all can use.Have in pigment used in the present invention, carbon black, phthalocyanine blue, phthalocyanine green, anthraquinone dye, scarlet 2b pigment lake, azo-compound, acid azo pigment, quinacridone, chromophthalocyanine pyrrols (chromophthalocyanine pyrrols), halogenated phthalocyanines, quinoline, heterocyclic dye, purple ketone (perinone) dyestuff, anthracenedione dyes, thioxanthene (thiozanthene) dyestuff, pyrazolone (parazolone) dyestuff, polymethine pigment and its combination.
This novel elastic composition of the present invention and comprise blend or the mixture of said composition, also can with other or additional additive or Compound Phase be combined, expect characteristic especially to provide to described composition.Many examples of such additives and compound are known in the art.Those skilled in the art knows use suitable additive or compound.This type of other or the example of additional additive or compound comprise UV stablizer, antioxidant, photostabilizer, fire retardant, static inhibitor, biocide, spices, viscosity breaking agent, impact modifying agent, softening agent, weighting agent, toughener, lubricant, releasing agent, whipping agent, nucleator etc.
Urethane of the present invention or copolyether ester or copolyether amide elastic composition can be made film or coated material.Film is manufactured by standard technique, comprise extrude, roll, film casting and blowing.Coated material is manufactured by standard technique, comprises solvent polymeric, letex polymerization, spraying dry and polycomponent mixing and coating.
The film of the elastic composition containing urethane of the present invention or copolyether ester or copolyether amide can be applied as being laminated on fabric, foam, leather and metal in goods.The limiting examples of these application comprises waterproof breathable cloth, tick and medical inspection and surgical glove.Coating containing urethane of the present invention or conjugated polyether ester elastomer composition can be used by fabric converter or dip coaterd.Limiting examples of these application comprise the wet method of fabric or dry coating, for the manufacture of the fabric of leatheroid or the condensation coating of non-woven base material and the dip-coating for the production of gloves and similar protector.
Usually can prepare the urethane or copolyether ester or copolyether amide elastic composition that contain the glycol obtained by oxirane and tetrahydrofuran by polymerization as described below, described oxirane has 2 to 4 carbon atoms.
cast polyurethane (CPU)
Cast polyurethane by by reactive fluid component pressurization or with no pressure and heating or do not heat mixing prepare to prepare homogeneous mass, described homogeneous mass is polymerized to generate elastomeric article more than room temperature.Described component typical case comprises the part containing isocyanic ester and the part that can react with isocyanate groups as diamines or glycol.Stirring can, to carry out from the speed of 10 to about 300rpm, make exothermic heat of reaction be no more than 80 DEG C.Reactor can be heated to the temperature of 70 DEG C to 80 DEG C, until reach target residual isocyanate content.Described residual isocyanate content is from 1 to 15% and represents the weight percent of contained isocyanate groups (N=C=O) given prepolymer species.Reactive material being cooled to temperature is from 50 DEG C to 60 DEG C, removes gas and is delivered to sealed vessel.Obtained wherein NCO group is the solid resin of about 1.03 to about 1.06 to OH group ratio.By being merged by the diamine chain stretching agent of prepolymer and necessary amount, prepare final polymkeric substance.Described component by powerful mixing, degasification, be delivered to mould and high temperature 50 DEG C-130 DEG C solidification lengthen 15 minutes-24 hours time.Test sample is obtained from the film of gained.Note, chainextender can be selected from: amine, diamines, polyamines, alcohol, glycol, polyvalent alcohol and their combination.The limiting examples of the preparation method of cast polyurethane can be combined in this Lawrey etc., U.S. Patent number 7,511 by reference, and 111 and Suzuki etc., U.S. Patent number 7,601, finds in 793.The representative instance of cast urethane elastomer is pulley, print roller, scraper, energy-absorbing liner etc.
polyurethane dispersions (PUD)
Polyurethane dispersions is prepared by the reactant aqueous solution of the prepolymer of water dispersible and chainextender being generated the dispersion of polyether polyols with reduced unsaturation in water.The limiting examples of the preparation method of polyurethane dispersions can be combined in this Klingenberg etc., U.S. Patent number 7,432 by reference, and 068 and Gertzmann etc., U.S. Patent number 7,345, finds in 110.A limiting examples of manufacture polyurethane dispersions comprises the dimethylol propionic acid (DMPA) to prepolymer interpolation 1 to 10 % by weight.When reaching the terminal of remaining isocyanic ester, with in such as 3 ° of amine and described DMPA.Alternatively, add on a small quantity based on final solution volume from about 0.001 % by weight to lower than about 5 % by weight on a small quantity can be miscible with water polar solvent, such as N-Methyl pyrrolidone (NMP).With strong stirring, add the chilled aqueous solution of diamine chain stretching agent to described prepolymer.Allow described emulsifying soln, until its reversion (water-in-oil → oil-in-water), and obtain the dispersion of urethane in water.
thermoplastic polyurethane (TPU)
Thermoplastic polyurethane is prepared with the simple linear polymer generating limited molecular weight by merging polyvalent alcohol, vulcabond, chainextender and multiple additives.Heat and pressure impact under can make thermoplastic material, to flow and to form film or solid articles.In addition, described thermoplastic material dissolving can be made coating fluid in a solvent.The limiting examples of the preparation method of thermoplastic polyurethane can be combined in this Dewanjee etc., U.S. Patent number 7,417 by reference, and 094 and Vedula etc., U.S. Patent number 7,202, finds in 322.
copolyether ester (COPE)
Copolyether ester, can be called copolyesters at this, is that the commodity that can obtain from E.I.Du Pont Company are called
engineering thermoplastic's polymkeric substance.They are thermoplastic elastomers of residing Temperature displaying chemical solvent resistance and dimensional stability in such as automobile application.They are prepared to generate the segmented copolymer be made up of soft segment (polyvalent alcohol and dicarboxylic acid reaction product) and hard block (short-chain diol and dicarboxylic acid reaction product) by aromatic dicarboxylic acid or Equivalent being merged with long-chain polyhydric alcohol and short-chain diol.The limiting examples of the preparation method of copolyether ester being combined in this British Patent No. 682,866 and U.S. Patent number 2,744 by reference, can find in 087.Being combined in this comment paper of W.K.Witsiepe, Adv.Chem.Ser. by reference, 129, in 39 (1973), detail a kind of two-step synthesis method of these materials.
These copolyether esters are such as, by the polyvalent alcohol of catalyzer and necessary amount and aromatic diacid Equivalent (typically, dimethyl terephthalate (DMT)) and excessive chainextender being merged preparations.Described chainextender can be selected from: ethylene glycol, BDO, hydroxymethyl-cyclohexane, 1,3-PD and their combination.Once the transesterify of described diacid Equivalent completes, just temperature is increased to such as from about 240 DEG C to about 250 DEG C, and under reduced pressure removes excessive chainextender, until prove by the viscosity of reactive material the extent of polymerization reaching expection.Described polymkeric substance is shifted out reactor, and is comprised by the means be applicable to and extrude, to roll or melting treatment is carried out in blowing, to obtain film.
Embodiment
To more intactly understand invention that is described here and request protection with reference to following embodiment, described embodiment is not intended to the scope limiting application claims.In these embodiments, the method by being substantially equivalent to ASTM E96 measures water vapor transmission.The humidity that we use in our measurement according to ASTM E96 is 50% and temperature is 70 °F (21 DEG C).Described copolyether ester sample is the film that 2-3mil is thick by hot pressing, and each specimen test three times, reports average data in table 1 below.
Second-order transition temperature (Tg) is determined by differential scanning calorimeter (DSC) and dynamic mechanical analysis (DMA).For the sample occurring melting phasing in synthesis, namely demonstrate the sample of two second-order transition temperatures or very wide Tg, DMA is particularly useful.Use nucleus magnetic resonance (NMR) spectrum to determine the composition of elastomer sample.In order to these are measured, elastomer sample is dissolved in sym.-tetrachloroethane-D2.For measuring mechanical property, by elastomer sample compression moulding also following test: Shore hardness (ASTM D2240), tensile strength (ASTM D412), Young's modulus (ASTMD412), elongation at break (ASTM D412), tearing strength, the loss of Die C (ASTM D1938), Taber Abrasion (ASTM D1044) and Corrash-Burger torsional strength (ASTM D1043).
embodiment 1
According to being combined in this comment paper of W.K.Witsiepe by reference, Adv.Chem.Ser., 129, the formula described in 39 (1973) prepares copolyether ester sample.Synthesis is implemented in the stainless steel reactor of 1 liter.The first step be utilize tetra-n-butyl titanate catalyzer in temperature 190-210 DEG C carry out dimethyl terephthalate (DMT) (DMT), molecular weight is 2025g/mol and has poly-(oxygen ethylidene-co-oxygen tetramethylene ether) transesterify between glycol and BDO (BDO) of the long-chain of 49 % by mole of oxygen ethyleneethers.In second step, in the vacuum of 250 DEG C and about 100 microns Hg, the mutual-phenenyl two acid bromide two alcohol ester of the first step gained and copolyether terephthalate are final product by polycondensation.By NMR, determine that the content of polybutylene terephthalate (PBT) hard segment is 50 % by weight.
embodiment 2
Prepare copolyether ester sample by the same method in such as embodiment 1, difference is, the content of PBT hard segment is 40 % by weight.And the molecular weight of poly-(oxygen ethylidene-co-oxygen tetramethylene ether) glycol of the long-chain in the first step is 2100g/mol and has 69 % by mole of oxygen ethylidene.By NMR, determine that the content of PBT hard segment is 40 % by weight.
comparative example 1 and 2
Prepare copolyether ester sample by the same method in such as embodiment 1 and 2, difference is, polyvalent alcohol is the homopolymer PTMEG of 2000g/mol, and the content of PBT hard segment is respectively 40 % by weight and 50 % by weight.
comparative example 3 and 4
For these comparative examples, copolyether ester sample is two parts of business buying from Ashland Inc.
copolyether ester product.Two increment product have EOPPG block copolymerization ethoxylated polyhydric alcohol containing 36 % by mole of PPG as soft chain segment.For these comparative examples, hard segment contents is respectively 38 % by weight and 48 % by weight.
Table 1
(1) " SS " is soft chain segment
(2) poly-(oxygen ethylidene-co-oxygen tetramethylene ether) glycol 49 % by mole of oxygen ethylidene
(3) poly-(oxygen ethylidene-co-oxygen tetramethylene ether) glycol 69 % by mole of oxygen ethylidene
(4) segmented copolymer of EOPPG, has 36 % by mole of PEG
(5) H-22 wheel
(6) Corrash-Burger rigidity---torsional strength is tested
Data presentation in table 1, compared to other COPE material derived from equal polyether glycol PTMEG, reaches with the film containing EOTHF multipolymer of the present invention the moisture permeable significantly improved.Compared to by the obtained COPE material of the ethylene oxide-capped polypropylene glycol (EOPPG) as soft chain segment, use film of the present invention can obtain suitable or or even better moisture permeable.
Mechanical properties data in Table 1 also shows, the COPE material obtained by film of the present invention is except excellent moisture permeable, physical strength is obviously better than the material obtained by EOPPG, and similar or be better than the material that obtained by PTMEG in some composition.Physical strength and moisture permeable can by changing the composition of soft chain segment, i.e. molecular-weight average and EO combination rate, or the content of hard polyester segments or type are conditioned, to meet the particular requirement of final utilization application.
embodiment 3 (CPU film)
In order to prepare cast polyurethane (CPU) film, by necessary material, such as, a part of vulcabond is placed in by the container heated.Add foregoing polyvalent alcohol, described polyvalent alcohol is enough to di-isocyanate reaction to generate the prepolymer of the residual isocyanate content with required degree, stirs with 250rpm simultaneously, and the speed of adding makes exothermic heat of reaction be no more than 80 DEG C.After adding polyvalent alcohol, reactor is heated to temperature and is about 75 DEG C, until reach target residual isocyanate content.Described residual isocyanate content is about 10% and represents the weight percent of contained isocyanate groups (N=C=O) in given prepolymer species.Reactive material temperature is cooled to about 55 DEG C, removes gas and be delivered to sealed vessel.
By by the diamine chain stretching agent combination system of described prepolymer and necessary amount for final polymkeric substance.Described component by powerful mixing, degasification, be delivered to mould and in high temperature about 100 DEG C solidification time of about 12 hours.Test sample is obtained from the film of gained.Note, chainextender can be selected from: amine, diamines, polyamines, alcohol, glycol, polyvalent alcohol and their combination.
embodiment 4 (TPU film)
As in embodiment 3, prepare solid resin, wherein, the ratio of NCO group to OH group is 1.00 to 1.02.This material is granulated and melting treatment; with by extruding generation three kinds of films; have poly-(oxygen ethylidene-co-oxygen tetramethylene ether) glycol of 49 % by mole of oxygen ethylidene containing molecular weight 2025g/mol, the second contains the EOPPG block copolymerization ethoxylated polyhydric alcohol of 36 % by mole of PPG and the third contains homopolymer PTMEG.The film obtained by poly-(oxygen ethylidene-co-oxygen tetramethylene ether) glycol has better physical strength compared with the film obtained by EOPPG, and has better moisture permeable compared with the film obtained by equal polyalcohols PTMEG.
embodiment 5 (PUD and its cast film)
In order to manufacture polyurethane dispersions, manufacture prepolymer as described in Example 3 when adding dimethylol propionic acid (DMPA) of about 5 % by weight.When reaching the terminal of remaining isocyanic ester, with in 3 ° of amine and described DMPA.With strong stirring, add the chilled aqueous solution of diamine chain stretching agent to described prepolymer.Allow described emulsifying soln, until its reversion (water-in-oil → oil-in-water), and obtain the dispersion of urethane in water.
Use poly-(oxygen ethylidene-co-oxygen tetramethylene ether) glycol, all polyalcohols PTMEG and block co-polyether polyol E OPPG, prepare the film obtained by polyurethane dispersions.The film obtained by poly-(oxygen ethylidene-co-oxygen tetramethylene ether) glycol has better physical strength compared with the film obtained by EOPPG, and has better moisture permeable compared with the film obtained by equal polyalcohols PTMEG.
All patents, patent application, experimental procedure, priority document, paper, publication, handbook and other document quoted from this all intactly combine by reference, its degree disclosed in it content not with contradiction of the present invention, and be all in order to wherein such combination all authority of law of being allowed to and combine.
When listing numerical upper limits and numerical lower limits herein, the scope from any lower limit to any upper limit is expection.
Although illustrative embodiment of the present invention is specifically described, should be understood to, other variant various is obvious for those skilled in the art under the premise without departing from the spirit and scope of the present invention and can easily implements.Therefore, intention is the restriction of the embodiment that the scope of claim of the present invention is not set forth and specification sheets herein, but be comprise all contained in the present invention feature with patent novelty by claim interpretation, comprise all features will treated as its equivalents thereto by applicable those skilled in the art in the invention.
Claims (17)
1. a film, described film comprises elastic composition, described elastic composition comprise 20 to lower than 70 % by weight the first component polyvalent alcohol obtained by the random copolymerization of the oxirane and tetrahydrofuran (THF) with 2 to 4 carbon atoms, with the second component urethane, copolyether ester or the copolyether amide that are greater than 30 to 80 % by weight, described elastic composition has the steam permeating rate being greater than 250 grams-mil/square metre-day and the tensile strength being greater than 1500psi.
2. film according to claim 1, wherein, described first component polyvalent alcohol has 500 to 3000 daltonian molecular weight, and the oxirane combination rate of 20 to 75 % by mole.
3. film according to claim 1, described composition comprises the first component polyvalent alcohol obtained by the random copolymerization of the oxirane and tetrahydrofuran (THF) with 2 to 4 carbon atoms of 35 to 65 % by weight, and the second component copolyether amide of 35 to 65 % by weight.
4. film according to claim 1, wherein, described first component polyvalent alcohol is by the preparation of the step that comprises the following steps: the oxirane that tetrahydrofuran (THF) and at least one are had 2 to 4 carbon atoms by (a) contains the existence of the compound of hydrogen atoms at acid catalyst and at least one under, at the temperature polymerizations of 50 DEG C to 80 DEG C, to prepare polymer product mixture, described polymer product mixture comprises oligomeric cyclic ethers, copolyether glycol, at least one oxirane dipolymer and tetrahydrofuran (THF); B () be separating most tetrahydrofuran (THF) and described oxirane dipolymer at least partially from the described polymer product mixture of step (a), to prepare the crude product mixture comprising oligomeric cyclic ethers and copolyether glycol; And (c) is separated described oligomeric cyclic ethers at least partially from the described crude product mixture of step (b), to prepare the oligomeric cyclic ethers stream comprising oligomeric cyclic ethers and the product stream comprising described polyvalent alcohol.
5. film according to claim 4, wherein, the described oxirane in described polyvalent alcohol preparation process (a) is selected from: oxyethane; 1,2 epoxy prapane; 1，3-epoxypropane; 1,2-butylene oxide ring; 2,3-butylene oxide ring; 1,3-butylene oxide ring; And their combination.
6. film according to claim 4, wherein, the described compound containing hydrogen atoms in described polyvalent alcohol preparation process (a) is selected from: water; Ethylene glycol; BDO; Molecular weight is the daltonian polytetramethylene ether diol of 130 dalton to 400; Molecular weight is the daltonian copolyether glycol of 130 dalton to 400; And their combination.
7. film according to claim 6, wherein, the described compound containing hydrogen atoms is water.
8. film according to claim 4, wherein, the described acid catalyst in described polyvalent alcohol preparation process (a) is selected from: the natural or synthetic zeolite of acidifying natural clay, acidifying, the sheet silicate activated optionally by acid treatment, acidifying zirconium/tin sulphate cpd, be coated to the oxygen containing molybdenum comprising at least one catalytic activity on oxidation carrier and/or tungsten part compound, containing sulfonic polyalcohol catalyst and their combination.
9. film according to claim 4, wherein, described tetrahydrofuran (THF) component in described polyvalent alcohol preparation process (a) comprises at least one alkyl tetrahydro furans further, and described at least one alkyl tetrahydro furans is selected from: 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran and their combination.
10. film according to claim 4, wherein, described oxirane is oxyethane, and described acid catalyst comprises containing sulfonic polyalcohol catalyst, and the described compound containing hydrogen atoms is selected from: water; Ethylene glycol; BDO; Molecular weight is the daltonian polytetramethylene ether diol of 130 dalton to 400; Molecular weight is the daltonian copolyether glycol of 130 dalton to 400; And their combination.
11. films according to claim 1, wherein said second component is urethane.
12. films according to claim 1, wherein said urethane is selected from the group be made up of cast polyurethane, thermoplastic polyurethane and polyurethane dispersions.
13. films according to claim 1, wherein said second component is copolyether ester.
14. films according to claim 1, wherein said second component is copolyether amide.
15. films according to claim 1, the wherein said oxirane with 2 to 4 carbon atoms is oxyethane.
16. films according to claim 15, wherein said first component polyvalent alcohol has the oxyethane combination rate of 20 to 75 % by mole.
17. films according to claim 15, described composition comprises the first component polyvalent alcohol obtained by the random copolymerization of oxyethane and tetrahydrofuran (THF) of 35 to 65 % by weight, and the second component urethane of 35 to 65 % by weight, copolyether ester or copolyether amide.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906729A (en) * | 1988-08-05 | 1990-03-06 | E. I. Du Pont De Nemours And Company | Thermoplastic copolyetherester elastomers |
| US6994913B1 (en) * | 1999-09-30 | 2006-02-07 | Sekisui Chemical Co., Ltd. | Thermoplastic elastomer, use thereof, and process for producing the same |
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2009
- 2009-12-11 CN CN201410612755.7A patent/CN104371310A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906729A (en) * | 1988-08-05 | 1990-03-06 | E. I. Du Pont De Nemours And Company | Thermoplastic copolyetherester elastomers |
| US6994913B1 (en) * | 1999-09-30 | 2006-02-07 | Sekisui Chemical Co., Ltd. | Thermoplastic elastomer, use thereof, and process for producing the same |
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