CN105377933A - Soft thermoplastic polyurethane elastomers and process for their preparation - Google Patents
Soft thermoplastic polyurethane elastomers and process for their preparation Download PDFInfo
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- CN105377933A CN105377933A CN201480038740.2A CN201480038740A CN105377933A CN 105377933 A CN105377933 A CN 105377933A CN 201480038740 A CN201480038740 A CN 201480038740A CN 105377933 A CN105377933 A CN 105377933A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7685—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing two or more non-condensed aromatic rings directly linked to each other
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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Abstract
The present invention discloses a thermoplastic polyurethane comprising substantially no plasticizers and having a Shore A hardness of 60 or less, which is prepared by a one-step polymerization of i) linear polyol, ii) organic diisocyanate and iii) glycol chain extender mainly comprising ethylene glycol and/or 1,3-propanediol; wherein the linear polyol (i) has a number average molecular weight within the range of from 1.5 x 103 g/mol to 5.0 x 103 g/mol. The thermoplastic polyurethane of the present invention can be easily produced by conventional production methods, and the thermoplastic polyurethane thus produced can be molded to articles in practicable processing cycles. Moreover, the thermoplastic polyurethane articles have low shrinkage, have good low-temperature properties and good mechanical properties, and do not harden substantially at low temperature.
Description
Technical field
The present invention relates to a kind of single stage method preparing very soft Polyurethane Thermoplastic Elastomer (TPU), described Polyurethane Thermoplastic Elastomer does not substantially comprise softening agent and has the Shore A Hardness of less than 60, and it can be molded as TPU goods in the process-cycle of reality.
Background technology
Polyurethane Thermoplastic Elastomer (TPU) is known a very long time.They are industrially very important, because it combines the known advantage of good mechanical characteristics and cheap thermoplasticity processibility.The mechanical characteristics of wide region realizes by using various chemical component component.The summary of TPU, its characteristic and purposes is recorded in such as Kunststoffe68 (1978), and 819 or Kautschuk, Gummi, Kunststoffe35 (1982), in 568.
TPU is made up of polyvalent alcohol (being generally polyester polyol or polyether glycol), vulcabond (being generally organic diisocyanate) and short-chain diol (chainextender) usually.The hardness of TPU is determined primarily of the ratio of hard segment (being formed by the reaction of chainextender and vulcabond group) with soft chain segment (being formed by the reaction of polyvalent alcohol and vulcabond group).Make the hardness of TPU be reduced to the limit lower than 80 Shore A Hardness if reduce the amount of hard segment, then the product of gained is clamminess usually, and solidified nature is poor, shows the release property of going on business in Shooting Technique, and shows serious shrinkability.This TPU cannot ensure acceptable injection cycle number of times economically.
At present, the soft TPU on market is occupied an leading position by the soft TPU of plasticising.But the TPU of those plasticising shows many shortcomings.When the hardness of composition is increased to less desirable level, softening agent is understood frosting (bloom) or is oozed out from said composition (extract).The use of some softening agent has also been subject to the inspection of environment and toxicity aspect.Therefore, if also required physical features can be obtained without the need to softening agent, then eliminate in TPU composition and the demand of softening agent is considered to favourable usually.
Another kind of soft TPU is the soft TPU of not plasticizer-containing.But, although the product with the Shore A Hardness being less than 60 has high demand almost commercially not exist.Reason is that method mechanical characteristics that is too expensive or described TPU is not enough to commercially to survive.
US8183330B2 discloses a kind of TPU that is soft, not plasticizer-containing and preparation method thereof.This TPU have be less than 75, be preferably less than 70 and be most preferably less than 65 Shore A Hardness, and to be substantially free of and preferred not plasticizer-containing.It is made up of the raw material comprising hydroxy-end capped intermediate, and comprises the hard segment of 10-40 % by weight, and described intermediate is derived from the glycol of branching or comprises at least 2 different repeating units.
US6790916B2 disclose a kind of have 45 to 65 Shore A Hardness and can the preparation method of TPU of the easily demoulding.For this preparation method, what have employed complexity comprises prepolymerized three-step approach.
EP1932863A2 discloses a kind of soft TPU and preparation method thereof.Described TPU has the Shore A Hardness of 45 to 80 and good release property.It makes in one-step reaction, which uses the polyester glycol of branching.
US8138299B2 discloses a kind of not plasticizer-containing and has the TPU of the Shore A Hardness of 50 to 80.This TPU is made up of the raw material comprising two kinds of polyester glycols, wherein a kind of polyester glycol is based on butane-1,4-glycol and at least one have the other glycol of at least 5 carbon atoms, and another kind of polyester glycol has the other glycol of two or three carbon atoms based on butane-Isosorbide-5-Nitrae-glycol and at least one.
Summary of the invention
Therefore, the object of the invention is to use a kind of soft TPU preparation of customary preparation methods exploitation, its Shore A Hardness had is less than 60, preferably 55 to 30, even more preferably 55 to 35, and be substantially free of softening agent.As shown in embodiment, measure Shore A Hardness according to DIN53505.
The present invention also aims to provide the above-mentioned soft TPU being substantially free of softening agent, its can in the process-cycle of reality by injection moulding, to extrude or other molding methods carry out molding to obtain finished product.
The present inventor have been surprisingly found that, the TPU with the Shore A Hardness of less than 60 can be made up of straight chain polyalcohols, organic diisocyanate and glycol chain extender in single step reaction.Particularly, described single stage method comprises by polymerization following component and synthesizes TPU:i) straight chain polyalcohols, ii) organic diisocyanate and iii) mainly comprise ethylene glycol and/or 1, the glycol chain extender of ammediol, the number-average molecular weight of wherein said straight chain polyalcohols (i) is 1.5 × 10
3g/mol to 5.0 × 10
3in the scope of g/mol.
Also find that the TPU prepared thus can be molded as TPU particle in the process-cycle of reality.Although TPU composition of the present invention is very soft in essence, their advantage is to there is the trend adhered to mould hardly.Therefore, they injection moulding application in use be very favorable.In addition, by the TPU goods of molding, be there is good cold property and good mechanical characteristics, and at low temperatures (as lower than-10 DEG C) substantially non-sclerous.
Embodiment
In a first aspect, the invention provides a kind of single stage method preparing TPU, described TUP has less than 60, preferably 55 to 30, the even more preferably Shore A Hardness of 50 to 35, described method comprises by polymerization following component and synthesizes TPU:i) straight chain polyalcohols, ii) organic diisocyanate and iii) mainly comprise the glycol chain extender of ethylene glycol and/or 1,3-PD, the number-average molecular weight of wherein said straight chain polyalcohols (i) is 1.5 × 10
3g/mol to 5.0 × 10
3scope in.
In formed TPU, the content of hard segment is 5 % by weight to 14 % by weight, preferably 6 % by weight to 12 % by weight, and even more preferably 7 % by weight to 10 % by weight.
Straight chain polyalcohols (i) for the preparation of TPU of the present invention is selected from polyester polyol, polyether glycol, polycaprolactone polyol, polycarbonate polyol etc.Wherein, preferred polyester polyvalent alcohol and polyether glycol, and the polyester polyol more preferably obtained by dicarboxylic acid and glycol.
Dicarboxylic acid for the preparation of polyester polyol comprises aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid or its combination.Wherein, preferred aliphatic series dicarboxylic acid.The suitable aliphatic dicarboxylic acid that can use separately or as a mixture comprises 4 to 12 carbon atoms usually, and comprises: succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid etc.Hexanodioic acid is preferred acid.
Glycol for the preparation of polyester polyol comprises aliphatic diol or aromatic diol, or it combines, and preferably comprises 2 to 8 carbon atoms and the aliphatic diol of more preferably 2 to 6 carbon atoms.Some representative example of spendable aliphatic diol comprise ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol etc.
In a preferred embodiment, only use a kind of aliphatic dicarboxylic acid to prepare polyester polyol.In another preferred embodiment, use one or both aliphatic diols to prepare polyester polyol.Most preferably, polyester polyol is by hexanodioic acid and 1, ammediol obtains (gathers (1,3-propylene adipate) glycol, PPA), or by hexanodioic acid and ethylene glycol and BDO obtain (poly-(ethylidene 1,4-butylene adipate) glycol, PEBA).In PEBA, the mol ratio of ethylene glycol and BDO is preferably 0.5:1 to 1.5:1, is particularly preferably 0.75:1 to 1.25:1.
The number-average molecular weight of linear polyesters polyvalent alcohol is usually 1.5 × 10
3g/mol to 5.0 × 10
3scope in.In a preferred embodiment, straight chain polyalcohols is the polyester polyol obtained by a kind of aliphatic dicarboxylic acid and two kinds of aliphatic diols, and the number-average molecular weight had is 2.2 × 10
3to 4.0 × 10
3, and be more preferably 2.5 × 10
3to 3.5 × 10
3.In another preferred embodiment, straight chain polyalcohols is the polyester polyol obtained by a kind of aliphatic dicarboxylic acid and a kind of aliphatic diol, and the number-average molecular weight had is 1.5 × 10
3to 4.0 × 10
3, and be more preferably 1.8 × 10
3to 3.5 × 10
3.
Except as otherwise noted, the unit of all molecular weight of specifying herein is [g/mol], and is number average molecular (Mn).
Organic diisocyanate (ii) for the preparation of TPU of the present invention is aliphatic vulcabond or aromatic diisocyanate.Aliphatic vulcabond comprises trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene vulcabond and/or eight methylene diisocyanates, 2-methyl pentamethylene 1,5-vulcabond, 2-ethylbutylene 1,4-vulcabond, pentamethylene 1,5-vulcabond, butylidene Isosorbide-5-Nitrae-vulcabond.Aromatic diisocyanate comprises ditan 2,2 '-vulcabond, ditan 2,4 '-vulcabond and/or ditan 4,4 '-vulcabond (MDI), naphthylidene 1,5-vulcabond (NDI), toluene 2,4-vulcabond and/or toluene 2,6-vulcabond (TDI), 3,3 '-dimethyl diphenyl vulcabond, 1,2-diphenylethane vulcabond and/or phenylene vulcabond.
Although can aliphatic vulcabond be used, highly preferably aromatic diisocyanate.In an especially preferred embodiment, organic diisocyanate be comprise at least 90 % by weight, more preferably at least 95 % by weight, particularly preferably at least 99 % by weight 4, the vulcabond of 4 '-diphenylmethanediisocyanate (4,4 '-MDI).
Glycol chain extender (iii) for the preparation of TPU of the present invention is ethylene glycol or 1,3-PD, or its mixture.Except ethylene glycol and 1,3-PD, glycol chain extender also can comprise a small amount of BDO, 1,5-PD and/or 1,6-hexylene glycol, and such as, described amount is 10 % by mole of the total mole number being not more than chainextender used.But, highly preferably only make spent glycol and 1,3-PD as chainextender, and most preferably chainextender is ethylene glycol.
In an especially preferred embodiment, poly-(1,3-propylene adipate) glycol be used as component i), 4,4'-MDI is used as component ii), and ethylene glycol is used as component iii) prepare TPU of the present invention, the number-average molecular weight that wherein poly-(trimethylene adipic acid ester) glycol preferably has is greater than 1.5 × 10
3, and more preferably greater than 1.8 × 10
3.In yet another particularly preferred embodiment, poly-(ethylidene 1,4-butylene adipate) glycol be used as component i), 4,4'-MDI is used as component ii), and ethylene glycol is used as component iii) prepare TPU of the present invention, the number-average molecular weight that wherein poly-(ethylidene tetramethylene adipic acid ester) glycol preferably has is greater than 2.2 × 10
3, and more preferably greater than 2.5 × 10
3.
In above-mentioned two preferred embodiments, ethylene glycol is 1.0 % by weight to 2.8 % by weight, preferably 1.2 % by weight to 2.4 % by weight of TPU composition total weight as the consumption of chainextender, and most preferably is 1.4 % by weight to 2.0 % by weight.
Also can add a small amount of conventional monofunctional compound as chain terminator or demolding aids.The example of suitable monofunctional compound comprises alcohols (such as, octanol and stearyl alcohol) and amine (such as, butylamine and stearylamine).
Usual expectation uses catalyzer, as sub-tin carboxylate salt or other metal carboxylates and tertiary amine.The example of metal carboxylates catalysts comprises stannous octoate, dibutyl tin laurate, phenylmercuric propionate, lead octoate 36, ferric acetyl acetonade, magnesium acetylacetonate etc.The example of tertiary amine catalyst comprises triethylenediamine etc.The amount of one or more catalyzer described is lower, is generally the final TPU polymkeric substance that about 10 to about 100 weight part/1,000,000 weight parts are formed.
Except TPU component and catalyzer, also can add conventional auxiliary agent and/or additive.Some examples that can mention comprise lubricant and releasing agent, fire retardant, nucleator, oxidation stabilizer, hydrolysis stabilizer, dyestuff and pigment, mineral filler and/or organic filler and toughener.In a preferred embodiment, make with lubricator as fatty acid ester and/or fatty acid amide.In another preferred embodiment, use hydrolysis stabilizer as the aliphatic series of oligomeric aliphatic series or aromatic carbodiimide and/or polymerization or aromatic carbodiimide.In this article, the consumption " being substantially free of softening agent " and meaning softening agent is optionally less than 5 % by weight of the gross weight of TPU composition.But, in a further preferred embodiment, do not use softening agent.If TPU of the present invention is subject to thermal oxidation damage between its usage period, then can adds antioxidant, wherein preferably use phenol antioxidant.Or auxiliary agent and/or additive can be added in the reaction forming TPU in the second combined steps.
In order to prepare TPU, forming component can with such quantitative response, the equivalent molar ratio making the summation of NCO group and NCO reactive group (the OH group particularly in chainextender and polyvalent alcohol) is 0.9:1.0 to 1.1:1.0, be preferably 0.95:1.0 to 1.05:1.0, and be more preferably 0.97:1.0 to 1.03:1.0.
TPU of the present invention can be prepared continuously or in batches.The commercial run of the preparation TPU known most is belt method and forcing machine method.In the method, component i), ii) and iii) can or to add with any order simultaneously.In a preferred embodiment, component i) with component iii) carry out premix and merge and be fed in reactor as blend, and by component ii) add separately in reactor.Between polymerization period, usually temperature of reaction is controlled in the scope of about 100 DEG C to about 300 DEG C, preferably about 150 DEG C to about 230 DEG C.The TPU prepared thus is carried out cooling and granulation.Granulation is undertaken by any comminution granulation as known in the art.
In a second aspect of the present invention, provide the TPU prepared by aforesaid method, its Shore A Hardness had is less than 60, preferably 55 to 30, and more preferably 50 to 35.
In a third aspect of the present invention, provide the method using the TPU prepared by aforesaid method to prepare moulded parts.Such as, injection moulding can be used, extrude, roll or blowing to prepare moulded parts, and preferably injection moulding.The method utilizing TPU to prepare moulded parts by injection moulding comprises: TPU is heated above the temperature of its fusing point by (a); B the TPU of melting is injected mould by (); C TPU in mould is cooled to temperature lower than its solidification value to prepare moulded parts by (); And moulded parts takes out by (d) from mould.During Shooting Technique, TPU fast setting, and be therefore easy to take out from mould.
TPU of the present invention has good mechanical characteristics.Even if TPU of the present invention also has good elasticity performance (namely without soft chain segment crystallization) at low temperatures, it shows as in experience lower than 0 DEG C or even lower than after temperature for some time of-10 DEG C, the increase of hardness is less.
The present invention is described by following examples, embodiment only for illustration of object, and should not think scope of the present invention or its restriction of mode implemented.
embodiment
Following methods and standard are used for measuring each parameter and assessing.
Shore A Hardness
Measure Shore A Hardness according to DIN53505, wherein after making pressure foot and test sample contacts, within 3 seconds, read hardness value.Hereinafter, hardness is expressed as Shore A Hardness (3 seconds).
Tensile strength
Measure tensile strength according to DIN53504, wherein use S2 test rod to measure.
Elongation at break
Measure elongation at break according to DIN53504, wherein use S2 test rod to measure.
Abrasion loss
Abrasion loss is measured according to DIN53516.
After demoulding, all test samples are annealed 20 hours at 100 DEG C, then at 23 DEG C, nurses one's health at least 16 hours before test.
Hardness increase at low temperatures processes 48 hours under being confirmed as the low temperature of the above-mentioned test sample through annealing at-30 DEG C and at 23 DEG C, nurses one's health the hardness increased value after 24 hours subsequently.If the increase of Shore A Hardness is less than 5, is then defined as test sample and there is low hardness increase at low temperatures.
Embodiment 1
By 229.18g4,4 '-MDI, 35.18g ethylene glycol and 1000g are 3.0 × 10 by the mumber average molar mass of hexanodioic acid and ethylene glycol and BDO acquisition
3the polyester polyol (PEBA) of g/mol carries out processing to synthesize TPU in extruder, and wherein the mol ratio of ethylene glycol and BDO is 1:1.In addition, add 8g hydrolysis stabilizer (the oligomeric carbodiimide obtained by tetramethylxylene diisocyanate (TMXDI), such as purchased from the ElastostabH01 of BASF), the 2.54g antioxidant (hindered phenol obtained by tetramethyl xylene and polyoxyethylene glycol, such as purchased from the Irganox1010 of BASF) and 3.82g lubricant (based on the ester type waxes of montanic acid, such as, purchased from the LicowaxE of Clariant).Prepared TPU particle is converted into test sample by injection moulding.
Embodiment 2
By 184.15g4,4 '-MDI, 24.01g ethylene glycol and 1000g are 3.0 × 10 by the mumber average molar mass of hexanodioic acid and ethylene glycol and BDO acquisition
3the polyester polyol (PEBA) of g/mol carries out processing to synthesize TPU in extruder, and wherein the mol ratio of ethylene glycol and BDO is 1:1.In addition, add 8g hydrolysis stabilizer (the oligomeric carbodiimide obtained by TMXDI, such as purchased from the ElastostabH01 of BASF), the 2.43g antioxidant (hindered phenol obtained by tetramethyl xylene and polyoxyethylene glycol, such as purchased from the Irganox1010 of BASF) and 6.08g lubricant (based on the ester type waxes of montanic acid, such as, purchased from the LicowaxE of Clariant).Prepared TPU particle is converted into test sample by injection moulding.
Embodiment 3
By 163g4,4 '-MDI, 18.79g ethylene glycol and 1000g are 3.0 × 10 by the mumber average molar mass of hexanodioic acid and ethylene glycol and BDO acquisition
3the polyester polyol (PEBA) of g/mol carries out processing to synthesize TPU in extruder, and wherein the mol ratio of ethylene glycol and BDO is 1:1.In addition, add 8g hydrolysis stabilizer (the oligomeric carbodiimide obtained by TMXDI, such as purchased from the ElastostabH01 of BASF), the 2.38g antioxidant (hindered phenol obtained by tetramethyl xylene and polyoxyethylene glycol, such as purchased from the Irganox1010 of BASF) and 5.95g lubricant (based on the ester type waxes of montanic acid, such as, purchased from the LicowaxE of Clariant).Prepared TPU particle is converted into test sample by injection moulding.
In embodiment 1 to 3, the mechanical testing results of the sample of preparation is shown in Table 1.
Table 1
By during injection molding, can easily be taken out from mould by the sample of embodiment 1 to 3 preparation.As can be seen from Table 1, they all demonstrate the Shore A Hardness (3 seconds) being less than 60, and gratifying mechanical characteristics.In addition, after storing at low temperatures, they all demonstrate low hardness increases.
Embodiment 4
By 276.33g4, the mumber average molar mass that 4 '-MDI, 36.53g ethylene glycol and 1000g are obtained by hexanodioic acid and 1,3-PD is 2.0 × 10
3the polyester polyol (PPA) of g/mol carries out processing to synthesize TPU in extruder.In addition, add 8g hydrolysis stabilizer (the oligomeric carbodiimide obtained by TMXDI, such as purchased from the ElastostabH01 of BASF), the 2.64g antioxidant (hindered phenol obtained by tetramethyl xylene and polyoxyethylene glycol, such as purchased from the Irganox1010 of BASF) and 3.96g lubricant (based on the ester type waxes of montanic acid, such as, purchased from the LicowaxE of Clariant).Prepared TPU particle is converted into test sample by injection moulding.
Embodiment 5
By 229.53g4, the mumber average molar mass that 4 '-MDI, 24.93g ethylene glycol and 1000g are obtained by hexanodioic acid and 1,3-PD is 2.0 × 10
3the polyester polyol (PPA) of g/mol carries out processing to synthesize TPU in extruder.In addition, add 8g hydrolysis stabilizer (the oligomeric carbodiimide obtained by TMXDI, such as purchased from the ElastostabH01 of BASF), the 2.53g antioxidant (hindered phenol obtained by tetramethyl xylene and polyoxyethylene glycol, such as purchased from the Irganox1010 of BASF) and 6.31g lubricant (based on the ester type waxes of montanic acid, such as, purchased from the LicowaxE of Clariant).Prepared TPU particle is converted into test sample by injection moulding.
Embodiment 6
By 207.72g4, the mumber average molar mass that 4 '-MDI, 19.51g ethylene glycol and 1000g are obtained by hexanodioic acid and 1,3-PD is 2.0 × 10
3the polyester polyol (PPA) of g/mol carries out processing to synthesize TPU in extruder.In addition, add 8g hydrolysis stabilizer (the oligomeric carbodiimide obtained by TMXDI, such as purchased from the ElastostabH01 of BASF), the 2.47g antioxidant (hindered phenol obtained by tetramethyl xylene and polyoxyethylene glycol, such as purchased from the Irganox1010 of BASF) and 6.18g lubricant (based on the ester type waxes of montanic acid, such as, purchased from the LicowaxE of Clariant).Prepared TPU particle is converted into test sample by injection moulding.
In embodiment 4 to 6, the mechanical testing results of the sample of preparation is shown in Table 2.
Table 2
By during injection molding, can easily be taken out from mould by the sample of embodiment 4 to 6 preparation.As can be seen from Table 2, they all demonstrate the Shore A Hardness (3 seconds) being less than 60, and gratifying mechanical characteristics.In addition, after storing at low temperatures, they all demonstrate low hardness increases.
Claims (23)
1. a thermoplastic polyurethane, its substantially do not comprise softening agent and have according to DIN53505 record less than 60 Shore A Hardness, wherein after making pressure foot and test sample contacts, within 3 seconds, read hardness value, and described thermoplastic polyurethane is prepared by the single step reaction of following component: i) straight chain polyalcohols, ii) organic diisocyanate and iii) mainly comprise the glycol chain extender of ethylene glycol and/or 1,3-PD; The number-average molecular weight of wherein said straight chain polyalcohols (i) is 1.5 × 10
3g/mol to 5.0 × 10
3in the scope of g/mol.
2. thermoplastic polyurethane according to claim 1, wherein said thermoplastic polyurethane have according to DIN53505 record 55 to 30 Shore A Hardness, wherein make pressure foot with test sample contacts after within 3 seconds, read hardness value.
3. thermoplastic polyurethane according to claim 2, wherein said thermoplastic polyurethane have according to DIN53505 record 50 to 35 Shore A Hardness, wherein make pressure foot with test sample contacts after within 3 seconds, read hardness value.
4. thermoplastic polyurethane according to claim 1, wherein said straight chain polyalcohols is selected from polyester polyol and polyether glycol.
5. thermoplastic polyurethane according to claim 4, wherein said straight chain polyalcohols is selected from the polyester polyol obtained by aliphatic dicarboxylic acid and aliphatic diol.
6. thermoplastic polyurethane according to claim 5, wherein said aliphatic dicarboxylic acid is the aliphatic dicarboxylic acid with 4 to 12 carbon atoms.
7. thermoplastic polyurethane according to claim 6, wherein said aliphatic dicarboxylic acid is hexanodioic acid.
8. thermoplastic polyurethane according to claim 5, wherein said aliphatic diol has 2 to 8 carbon atoms.
9. thermoplastic polyurethane according to claim 8, wherein said aliphatic diol has 2 to 6 carbon atoms.
10. the thermoplastic polyurethane according to any one of claim 5 and 9, the aliphatic diol that wherein said polyester polyol has 2 to 6 carbon atoms by one or both is made.
11. thermoplastic polyurethanes according to any one of claim 1 and 5, wherein said polyester polyol is obtained by a kind of aliphatic dicarboxylic acid and two kinds of aliphatic diols, and the number-average molecular weight had is 2.2 × 10
3to 4.0 × 10
3, and be more preferably 2.5 × 10
3to 3.5 × 10
3.
12. thermoplastic polyurethanes according to any one of claim 1 and 5, wherein said polyester polyol is obtained by a kind of aliphatic dicarboxylic acid and a kind of aliphatic diol, and the number-average molecular weight had is 1.5 × 10
3to 4.0 × 10
3, and be more preferably 1.8 × 10
3to 3.5 × 10
3.
13. thermoplastic polyurethanes according to any one of claim 7 and 10, wherein said polyester polyol is by hexanodioic acid and 1, ammediol obtains (gathers (1,3-propylene adipate) glycol), or by hexanodioic acid and ethylene glycol and 1,4-butyleneglycol obtains (poly-(ethylidene tetramethylene adipic acid ester) glycol).
14. thermoplastic polyurethanes according to claim 1, wherein said organic diisocyanate is aromatic diisocyanate.
15. thermoplastic polyurethanes according to claim 14, wherein said organic diisocyanate is diphenylmethanediisocyanate.
16. thermoplastic polyurethanes according to claim 15, wherein said organic diisocyanate is 4,4 '-diphenylmethanediisocyanate.
17. thermoplastic polyurethanes according to claim 1, wherein said glycol chain extender is ethylene glycol.
18. thermoplastic polyurethanes according to any one of claim 1 and 4 to 17, wherein said glycol chain extender is ethylene glycol; Wherein said organic diisocyanate is 4,4 '-diphenylmethanediisocyanate; And wherein said straight chain polyalcohols is obtained (poly-(trimethylene adipic acid ester) glycol) by hexanodioic acid and 1,3-PD, and the number-average molecular weight had is 1.5 × 10
3to 4.0 × 10
3, and be more preferably 1.8 × 10
3to 3.5 × 10
3.
19. thermoplastic polyurethanes according to any one of claim 1 and 4 to 17, wherein said glycol chain extender is ethylene glycol; Wherein said organic diisocyanate is 4,4 '-diphenylmethanediisocyanate; And wherein said straight chain polyalcohols is obtained (poly-(ethylidene tetramethylene adipic acid ester) glycol) by hexanodioic acid and ethylene glycol and BDO, and the number-average molecular weight had is 2.2 × 10
3to 4.0 × 10
3, and be more preferably 2.5 × 10
3to 3.5 × 10
3.
20. according to claim 17 to the thermoplastic polyurethane according to any one of 19, and wherein ethylene glycol is 1.0 % by weight to 2.8 % by weight of described thermoplastic polyurethane gross weight as the consumption of chainextender.
21. thermoplastic polyurethanes according to claim 20, wherein the consumption of ethylene glycol is 1.2 % by weight to 2.4 % by weight of described thermoplastic polyurethane gross weight.
22. thermoplastic polyurethanes according to claim 21, wherein the consumption of ethylene glycol is 1.4 % by weight to 2.0 % by weight of described thermoplastic polyurethane gross weight.
23. 1 kinds of methods preparing the moulded parts of thermoplastic polyurethane, it comprises by injection moulding or extrudes the thermoplastic polyurethane according to any one of claim 1 to 22 is carried out molding.
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| PCT/EP2014/061120 WO2014195211A1 (en) | 2013-06-04 | 2014-05-28 | Soft thermoplastic polyurethane elastomers and process for their preparation |
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| CN110809591A (en) * | 2017-06-26 | 2020-02-18 | 巴斯夫欧洲公司 | Thermoplastic polyurethanes |
| CN115260429A (en) * | 2021-11-10 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Polyether composition, thermoplastic polyurethane and preparation method thereof |
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| CN115260437B (en) * | 2022-07-29 | 2023-08-29 | 美瑞新材料股份有限公司 | Mobile phone protective sleeve not easy to turn yellow in actual use and manufacturing method thereof |
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| CN115260429A (en) * | 2021-11-10 | 2022-11-01 | 佳化化学科技发展（上海）有限公司 | Polyether composition, thermoplastic polyurethane and preparation method thereof |
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| KR20160018659A (en) | 2016-02-17 |
| KR102308489B1 (en) | 2021-10-07 |
| CN112876648B (en) | 2023-05-05 |
| CN105377933B (en) | 2021-11-02 |
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