CN107141441A - A kind of low-refraction high transparency TPUE and preparation method thereof - Google Patents
A kind of low-refraction high transparency TPUE and preparation method thereof Download PDFInfo
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- CN107141441A CN107141441A CN201710408099.2A CN201710408099A CN107141441A CN 107141441 A CN107141441 A CN 107141441A CN 201710408099 A CN201710408099 A CN 201710408099A CN 107141441 A CN107141441 A CN 107141441A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy 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
- C08G18/70—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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/7642—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 containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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- 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
- 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
- C08G18/7664—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
Abstract
The invention provides a kind of low-refraction high transparency TPUE and preparation method thereof.The raw material of the polyurethane elastomer includes the component of following mass fraction：0.1 1 parts of 25 40 parts of diisocyanate, 60 75 parts of PPG, 10 25 parts of chain extender and catalyst；The diisocyanate includes at least asymmetric diisocyanate of 50wt% structure, and the average functionality of the chain extender is more than 2.The preparation method is：First by the diisocyanate of formula ratio, PPG and catalyst hybrid reaction, base polyurethane prepolymer for use as is made, then base polyurethane prepolymer for use as is mixed with chain extender, stands reaction, obtains the TPUE.The TPUE that the present invention is provided is while have relatively low refractive index, higher light transmittance and good mechanical performance.
Description
Technical field
The invention belongs to TPUE technical field, and in particular to a kind of transparent thermoplastic polyurethane elasticity
Body and preparation method thereof, more particularly to a kind of low-refraction high transparency TPUE and preparation method thereof.
Background technology
TPUE (TPU) is because with good tensile strength, tearing toughness, impact resistance, wear-resisting
The advantages of property, weatherability, hydrolytic resistance and oil resistivity, it is widely used in flexible pipe, packing ring, wheel belt, roller, gear, pipeline etc.
Protection, insulator, in terms of sole and solid tyre.Transparent TPU is one kind of TPU materials, because with higher printing opacity
Rate, is widely used in terms of sole, wheel for roller skates, ophthalmic len, printer or electronic photographing device.
TPU is a kind of block copolymerization Linear high-molecular compound being made up of soft segment and hard section.Due to hard section and soft segment
Thermodynamics is incompatible, therefore the micro phase separation structure that TPU is separated with relatively more special hard section and soft segment.Soft segment assigns product
The performance such as flexible, resilience and flexibility, hard section assigns the excellent mechanical performance of product and chemical-resistant.
Normally transparent TPU application field requires that it has high transmission rate and high mechanical properties concurrently, some electronic equipments should
Also require that it has relatively low refractive index reflective to reduce with field.And transparent TPU materials are obtained, it must just destroy material
Crystallinity, but this can cause the mechanical strength of material to decline again.Therefore the light transmittance and mechanical strength of existing transparent TPU are often
It is difficult to take into account.
At present, the fundamental research work to TPU aggregated structures and property relationship lays particular emphasis on nontransparent system more, and
To transparent polyurethane elastomer, optical requirement field is referred to, performance requirement is higher, it is synthesized, theoretical research aspect is reported
It is less, the fundamental research Comparision of aggregated structure and performance is weak, and the depth of investigation and width are also far from enough.
Therefore, the light transmittance and mechanical strength of TPU materials how are improved simultaneously, are that this area technology urgently to be resolved hurrily is asked
Topic.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide a kind of transparent thermoplastic polyurethane elastomer
And preparation method thereof, especially it is to provide a kind of low-refraction high transparency TPUE and preparation method thereof.The heat
Plastic polyurethane elastomer has higher light transmittance and good mechanical performance simultaneously.
For up to this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of transparent thermoplastic polyurethane elastomer, and its raw material includes following mass fraction
Component：
25-40 parts of diisocyanate for example can be 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, 36 parts,
38 parts or 40 parts etc.；
60-75 parts of PPG for example can be 60 parts, 62 parts, 64 parts, 65 parts, 66 parts, 68 parts, 70 parts, 72 parts,
74 parts or 75 parts etc.；
10-25 parts of chain extender, for example, can be 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts
Or 25 parts etc.；
With 0.1-1 parts of catalyst, for example can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part,
0.8 part, 0.9 part or 1 part etc.；
The diisocyanate comprising at least 50wt% (such as 50wt%, 55wt%, 60wt%, 65wt%, 70wt%,
75wt%, 80wt%, 85wt%, 90wt% or 100wt% etc.) the asymmetric diisocyanate of structure, the chain extender
Average functionality is more than 2.
The present invention destroys the regularity of rigid polyurethane segment by using the asymmetric diisocyanate of structure；Using average
The chain extender that degree of functionality is more than 2 makes polyurethane occur a certain degree of crosslinking, hinders the formation of hydrogen bond between hard segment, reduces microfacies
Separation degree.The two collective effect, can reduce the crystallinity of polyurethane, so as to improve its light transmittance.But rigid polyurethane chain
After the regularity of section is destroyed, the decline of polyurethane mechanical strength can be caused, and be crosslinked and then compensate for mechanicalness loss of energy, from
And make obtained TPU that also there is good mechanical performance.
Preferably, the diisocyanate by 50-80wt% (such as 50wt%, 52wt%, 55wt%, 58wt%,
60wt%, 62wt%, 65wt%, 68wt%, 70wt%, 72wt%, 75wt%, 78wt% or 80wt% etc.) structure it is not right
Title diisocyanate and 20-50wt% (such as 20wt%, 22wt%, 25wt%, 28wt%, 30wt%, 32wt%,
35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 48wt% or 50wt% etc.) symmetrical configuration diisocyanate group
Into.
Although being favorably improved the light transmittance of polyurethane using the asymmetric diisocyanate of structure, its content is excessive
The decline of mechanical performance can be caused.By controlling its ratio to be 50-80wt%, it ensure that obtained TPU has well saturating
While lightness, mechanical strength is further enhanced.
Preferably, the asymmetric diisocyanate of the structure is selected from IPDI (IPDI), 1,3- rings
Hexane dimethylene diisocyanate (1,3-H6XDI), m-xylylene diisocyanate (1,3-XDI), 2,4'- diphenyl
Methane diisocyanate (2,4'-MDI) or one kind in toluene di-isocyanate(TDI) (TDI) or at least two combination.
Preferably, the asymmetric diisocyanate of the structure includes at least 80wt% IPDI.
Preferably, the asymmetric diisocyanate of the structure by 80-95wt% (such as 80wt%, 81wt%,
82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, 92wt%,
93wt%, 94wt% or 95wt% etc.) IPDI and 5-20wt% (such as 5wt%, 6wt%, 8wt%, 10wt%, 12wt%,
14wt%, 15wt%, 16wt%, 18wt% or 20wt% etc.) 2,4'-MDI composition.
IPDI is the asymmetric alicyclic diisocyanate of structure, compared to aromatic diisocyanate, by IPDI systems
Standby TPU has relatively low refractive index, and light transmittance is further improved, but mechanical strength declines.The present invention is by selecting IPDI
It is engaged with 2,4'-MDI under specific ratio, the TPU enabled to is with relatively low refractive index, and light transmittance and machine
Tool intensity is further enhanced.
Preferably, the diisocyanate of the symmetrical configuration be selected from Isosorbide-5-Nitrae-cyclohexanedimethyleterephthalate diisocyanate (Isosorbide-5-Nitrae-
H6XDI), terephthalylidene diisocyanate (1,4-XDI), 4,4'- methyl diphenylene diisocyanates (4,4'-MDI), 4,
4'- dicyclohexyl methyl hydride diisocyanates (4,4'-H12MDI) or one kind in hexamethylene diisocyanate (HDI) or at least
Two kinds of combination.
Preferably, the diisocyanate of the symmetrical configuration includes at least the 4,4'-H12MDI of 80wt%.
Preferably, the diisocyanate of the symmetrical configuration by 80-90wt% (such as 80wt%, 81wt%, 82wt%,
83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt% or 90wt% etc.) 4,4'-H12MDI and 10-
20wt% (such as 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt% or 20wt%) 1,4-XDI compositions.
Cooperated using 4,4'-H12MDI and Isosorbide-5-Nitrae-XDI under specific ratio, help further to reduce TPU's
Refractive index, improves its light transmittance and mechanical strength.
Preferably, the number-average molecular weight of the PPG is 1000-3000；For example can be 1000,1200,
1500th, 1800,2000,2200,2500,2800 or 3000 etc..
The molecular weight of PPG should be maintained in suitable scope, when its molecular weight is excessive, can cause TPU soft chain segments
Excessively submissive, crystallinity increase, light transmittance declines；When its molecular weight is too small, the rigidly increase of TPU soft chain segments can be caused, impact is strong
Degree and flexibility decrease.
Preferably, the PPG is selected from polytetrahydrofuran diol (PTMG), polyoxypropyleneglycol (PPG) or poly-
One kind or at least two combination in ethylene glycol (PEG).
Preferably, the PPG includes at least 60wt% polyoxypropyleneglycol.
Preferably, the PPG by 60-80wt% (such as 60wt%, 62wt%, 65wt%, 68wt%,
70wt%, 72wt%, 75wt%, 78wt% or 80wt% etc.) polyoxypropyleneglycol and 20-40wt% (such as 20wt%,
22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt% or 40wt% etc.) polytetrahydrofuran diol group
Into.
PPG has rigid side base, helps to reduce TPU crystallinity, improves light transmittance, it can also cause TPU is rushed
The decline of hit intensity.PPG and PTMG is cooperated under specific ratio, the TPU enabled to has higher printing opacity
Rate and mechanical strength.
Preferably, the chain extender comprising 20-30wt% (such as 20wt%, 21wt%, 22wt%, 23wt%,
24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt% or 30wt% etc.) three-functionality-degree small molecule alcohol.
The small molecule alcohol of the three-functionality-degree of certain consumption can crosslink TPU, and transparency and mechanical strength are improved,
But when its consumption is excessive, it is excessive to be easily caused TPU hardness, elasticity and impact strength decreased, or even loses the effect of elastomer.
Preferably, the chain extender also comprising 70-80wt% (such as 70wt%, 71wt%, 72wt%, 73wt%,
74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt% or 80wt% etc.) small molecule glycol.
Preferably, the small molecule alcohol of the three-functionality-degree is trimethylolpropane.
Preferably, the small molecule glycol is selected from ethylene glycol, BDO or one kind in 1,6- hexylene glycol or at least
Two kinds of combination.
Preferably, the one kind or at least two of the catalyst in organotin, organo-bismuth, Organic leadP or amines catalyst
The combination planted.
Preferably, the catalyst is organotin catalysts.
Preferably, the organotin catalysts are dibutyl tin laurate and/or stannous octoate.
On the other hand, the present invention provides a kind of above-mentioned transparent thermoplastic polyurethane method for producing elastomers, including as follows
Step：
(1) diisocyanate, PPG and catalyst of formula ratio are mixed, reaction obtains base polyurethane prepolymer for use as；
(2) base polyurethane prepolymer for use as is mixed with the chain extender of formula ratio, stands reaction, obtain the transparent thermoplastic
Polyurethane elastomer.
Preferably, the preparation method be additionally included in before step (1) to the diisocyanate, PPG and
Processing is dried in chain extender.
Preferably, reaction is to carry out under agitation described in step (1).
Preferably, the rotating speed of the stirring is 150-300r/min；For example can be 150r/min, 180r/min, 200r/
Min, 220r/min, 250r/min, 280r/min or 300r/min etc..
Preferably, the temperature reacted described in step (1) is 70-100 DEG C, and the time of the reaction is 0.5-2h；For example
Can be 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.8h or 2h etc..
Preferably, step (1) is additionally included in progress deaeration processing after reaction terminates.
Preferably, mixing is to carry out under agitation described in step (2).
Preferably, the rotating speed of the stirring is 200-300r/min, for example, can be 200r/min, 220r/min, 250r/
Min, 280r/min or 300r/min etc.；The time of the stirring be 10-20s, for example can be 10s, 11s, 12s, 13s,
14s, 15s, 16s, 17s, 18s, 19s or 20s etc..
Preferably, the temperature reacted described in step (2) is 90-120 DEG C, for example can be 90 DEG C, 92 DEG C, 95 DEG C, 98
DEG C, 100 DEG C, 102 DEG C, 105 DEG C, 108 DEG C, 110 DEG C, 112 DEG C, 115 DEG C, 118 DEG C or 120 DEG C etc.；The time of the reaction is
1-3h, such as can be 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h or 3h.
Preferably, the preparation method comprises the following steps：
(1) processing is dried to the diisocyanate, PPG and chain extender；
(2) diisocyanate, PPG and catalyst of dry formula ratio are mixed, keeping temperature is 70-100
DEG C, obtain base polyurethane prepolymer for use as after stirring reaction 0.5-2h, deaeration under 150-300r/min rotating speed；
(3) chain extender of the formula ratio by the base polyurethane prepolymer for use as with drying is stirred under 200-300r/min rotating speed
10-20s is mixed, reaction 0.5-2h is stood at 90-120 DEG C, the transparent thermoplastic polyurethane elastomer is obtained.
Compared with prior art, the invention has the advantages that：
The present invention destroys the regularity of rigid polyurethane segment by using the asymmetric diisocyanate of structure；Using average
The chain extender that degree of functionality is more than 2 makes polyurethane occur a certain degree of crosslinking, hinders the formation of hydrogen bond between hard segment, reduces microfacies
Separation degree.The two collective effect, can reduce the crystallinity of polyurethane, so as to improve its light transmittance, and make it have good
Good mechanical performance.
Light transmittance >=93% for the TPU materials that the present invention is provided, hardness (shore A) is 74-85, and tensile strength is 24-
32MPa, elongation at break is 520-600%, and tearing strength is 58-65kN/m.
It is preferred by being carried out to diisocyanate, PPG and chain extender, the refractive index of TPU materials can be reduced,
And further improve its light transmittance and mechanical strength.Its refractive index is 1.36-1.44, light transmittance >=95%, and hardness (shore A) is
81-85, tensile strength is 30-32MPa, and elongation at break is 520-550%, and tearing strength is 62-65kN/m.
Embodiment
Technical scheme is further illustrated below by specific embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Embodiment 1
A kind of transparent thermoplastic polyurethane elastomer, its raw material includes the component of following mass fraction：
25 parts of diisocyanate (16 parts of IPDI, 4 parts of 2,4'-MDI, 4 parts of 4,4'-H12MDI and 1 part of Isosorbide-5-Nitrae-XDI), polyethers
75 parts of polyalcohol (60 parts of PPG and 15 part of PTMG), 10 parts of chain extender (3 parts of trimethylolpropanes and 7 parts of BDOs) and 0.1
Part catalyst (dibutyl tin laurate)；
Wherein, PPG and PTMG number-average molecular weight is 2000.
Above-mentioned transparent thermoplastic polyurethane method for producing elastomers comprises the following steps：
(1) processing is dried to diisocyanate, PPG and chain extender；
(2) diisocyanate, PPG and catalyst of dry formula ratio are mixed, keeping temperature is 70 DEG C,
Under 300r/min rotating speed base polyurethane prepolymer for use as is obtained after stirring reaction 0.5h, deaeration；
(3) chain extender of the formula ratio by above-mentioned base polyurethane prepolymer for use as with drying is stirred under 300r/min rotating speed mixes
10s, reaction 0.5h is stood at 120 DEG C, above-mentioned transparent thermoplastic polyurethane elastomer is obtained.
Embodiment 2
A kind of transparent thermoplastic polyurethane elastomer, its raw material includes the component of following mass fraction：
40 parts of diisocyanate (19 parts of IPDI, 1 part of 2,4'-MDI, 18 parts of 4,4'-H12MDI and 2 part of Isosorbide-5-Nitrae-XDI), polyethers
60 parts of polyalcohol (36 parts of PPG and 24 part of PTMG), 25 parts of chain extender (5 parts of trimethylolpropanes and 20 parts of 1,6- hexylene glycols) and 1
Part catalyst (stannous octoate)；
Wherein, PPG and PTMG number-average molecular weight is 2000.
Above-mentioned transparent thermoplastic polyurethane method for producing elastomers comprises the following steps：
(1) processing is dried to diisocyanate, PPG and chain extender；
(2) diisocyanate, PPG and catalyst of dry formula ratio are mixed, keeping temperature is 100 DEG C,
Under 150r/min rotating speed base polyurethane prepolymer for use as is obtained after stirring reaction 2h, deaeration；
(3) chain extender of the formula ratio by above-mentioned base polyurethane prepolymer for use as with drying is stirred under 200r/min rotating speed mixes
20s, reaction 2h is stood at 90 DEG C, above-mentioned transparent thermoplastic polyurethane elastomer is obtained.
Embodiment 3
A kind of transparent thermoplastic polyurethane elastomer, its raw material includes the component of following mass fraction：
30 parts of diisocyanate (18 parts of IPDI, 3 parts of 2,4'-MDI, 7.5 parts of 4,4'-H12MDI and 1.5 part of Isosorbide-5-Nitrae-XDI),
70 parts of PPG (49 parts of PPG and 21 part of PTMG), 20 parts of chain extender (5 parts of trimethylolpropanes and 15 parts of ethylene glycol) and
0.5 part of catalyst (dibutyl tin laurate)；
Wherein, PPG and PTMG number-average molecular weight is 2000.
Above-mentioned transparent thermoplastic polyurethane method for producing elastomers comprises the following steps：
(1) processing is dried to diisocyanate, PPG and chain extender；
(2) diisocyanate, PPG and catalyst of dry formula ratio are mixed, keeping temperature is 80 DEG C,
Under 200r/min rotating speed base polyurethane prepolymer for use as is obtained after stirring reaction 1h, deaeration；
(3) chain extender of the formula ratio by above-mentioned base polyurethane prepolymer for use as with drying is stirred under 250r/min rotating speed mixes
15s, reaction 1.5h is stood at 100 DEG C, above-mentioned transparent thermoplastic polyurethane elastomer is obtained.
Embodiment 4
A kind of transparent thermoplastic polyurethane elastomer, its raw material includes the component of following mass fraction：
35 parts of diisocyanate (25.2 parts of IPDI, 2.8 parts of 2,4'-MDI, 6.3 parts of 4,4'-H12MDI and 0.7 part of 1,4-
XDI), 65 parts of PPG (47 parts of PPG and 13 part of PTMG), 15 parts of chain extender (3 parts of trimethylolpropanes and 12 parts of 1,6- oneself
Glycol) and 0.8 part of catalyst (dibutyl tin laurate)；
Wherein, PPG and PTMG number-average molecular weight is 2000.
Above-mentioned transparent thermoplastic polyurethane method for producing elastomers comprises the following steps：
(1) processing is dried to diisocyanate, PPG and chain extender；
(2) diisocyanate, PPG and catalyst of dry formula ratio are mixed, keeping temperature is 90 DEG C,
Under 250r/min rotating speed base polyurethane prepolymer for use as is obtained after stirring reaction 1.5h, deaeration；
(3) chain extender of the formula ratio by above-mentioned base polyurethane prepolymer for use as with drying is stirred under 200r/min rotating speed mixes
12s, reaction 1h is stood at 110 DEG C, above-mentioned transparent thermoplastic polyurethane elastomer is obtained.
Embodiment 5
A kind of transparent thermoplastic polyurethane elastomer, its raw material includes the component of following mass fraction：
30 parts of diisocyanate (20 parts of IPDI, 4 parts of 2,4'-MDI, 5 parts of 4,4'-H12MDI and 1 part of Isosorbide-5-Nitrae-XDI), polyethers
70 parts of polyalcohol (56 parts of PPG and 14 part of PTMG), 18 parts of chain extender (4 parts of trimethylolpropanes and 14 parts of BDOs) and
0.3 part of catalyst (stannous octoate)；
Wherein, PPG and PTMG number-average molecular weight is 2000.
Above-mentioned transparent thermoplastic polyurethane method for producing elastomers comprises the following steps：
(1) processing is dried to diisocyanate, PPG and chain extender；
(2) diisocyanate, PPG and catalyst of dry formula ratio are mixed, keeping temperature is 85 DEG C,
Under 200r/min rotating speed base polyurethane prepolymer for use as is obtained after stirring reaction 1h, deaeration；
(3) chain extender of the formula ratio by above-mentioned base polyurethane prepolymer for use as with drying is stirred under 300r/min rotating speed mixes
18s, reaction 1.5h is stood at 120 DEG C, above-mentioned transparent thermoplastic polyurethane elastomer is obtained.
Embodiment 6
Difference with embodiment 1 is, diisocyanate by 15 parts of IPDI, 5 parts of 2,4'-MDI, 3 parts of 4,4'-H12MDI and
2 parts of Isosorbide-5-Nitrae-XDI, other raw material dosages and preparation method are same as Example 1.
Embodiment 7
Difference with embodiment 1 is, diisocyanate by 19.5 parts of IPDI, 0.5 part 2,4'-MDI and 5 part 4,4'-
H12MDI is constituted, and other raw material dosages and preparation method are same as Example 1.
Embodiment 8
Difference with embodiment 1 is that PPG is made up of 65 parts of PPG and 10 part of PTMG, other raw material dosages and
Preparation method is same as Example 1.
Embodiment 9
Difference with embodiment 1 is that PPG is made up of 40 parts of PPG and 35 part of PTMG, other raw material dosages and
Preparation method is same as Example 1.
Embodiment 10
Difference with embodiment 1 is that chain extender is made up of 1 part of trimethylolpropane and 9 parts of BDOs, and other are former
Expect that consumption and preparation method are same as Example 1.
Embodiment 11
Difference with embodiment 1 is that chain extender is made up of 4 parts of trimethylolpropanes and 6 parts of BDOs, and other are former
Expect that consumption and preparation method are same as Example 1.
Comparative example 1
Difference with embodiment 1 is, diisocyanate by 4 parts of IPDI, 1 part of 2,4'-MDI, 16 parts of 4,4'-H12MDI and
4 parts of Isosorbide-5-Nitrae-XDI compositions, other raw material dosages and preparation method are same as Example 1.
Comparative example 2
Difference with embodiment 1 is that chain extender is BDO.
The performance data and testing standard for the TPU that above-described embodiment 1-11 and comparative example 1-2 is provided are as shown in table 1 below.
Table 1
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can be readily occurred in, within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of transparent thermoplastic polyurethane elastomer, it is characterised in that the raw material of the transparent thermoplastic polyurethane elastomer
Include the component of following mass fraction：
0.1-1 parts of 25-40 parts of diisocyanate, 60-75 parts of PPG, 10-25 parts of chain extender and catalyst；
The diisocyanate includes at least asymmetric diisocyanate of 50wt% structure, the average function of the chain extender
Degree is more than 2.
2. transparent thermoplastic polyurethane elastomer according to claim 1, it is characterised in that the diisocyanate by
The 50-80wt% asymmetric diisocyanate of structure and the diisocyanate of 20-50wt% symmetrical configuration composition.
3. transparent thermoplastic polyurethane elastomer according to claim 1 or 2, it is characterised in that the structure is asymmetric
Diisocyanate be selected from IPDI, 1,3- cyclohexanedimethyleterephthalates diisocyanate, m-phenylenedimethylim-
Diisocyanate, 2,4'- methyl diphenylene diisocyanates or one kind in toluene di-isocyanate(TDI) or at least two combination；
Preferably, the asymmetric diisocyanate of the structure includes at least 80wt% IPDI；
Preferably, the asymmetric diisocyanate of the structure by 80-95wt% IPDI and 5-
20wt% 2,4'- methyl diphenylene diisocyanates composition.
4. the transparent thermoplastic polyurethane elastomer according to claim any one of 1-3, it is characterised in that the structure pair
The diisocyanate of title is selected from 1,4- cyclohexanedimethyleterephthalates diisocyanate, terephthalylidene diisocyanate, 4,4'- bis-
Methylenebis phenyl isocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates or one kind in hexamethylene diisocyanate or
At least two combination；
Preferably, the diisocyanate of the symmetrical configuration includes at least 80wt% isocyanic acid of 4,4'- dicyclohexyl methyl hydrides two
Ester；
Preferably, the diisocyanate of the symmetrical configuration by 80-90wt% 4,4'- dicyclohexyl methyl hydride diisocyanates and
10-20wt% terephthalylidene diisocyanate composition.
5. the transparent thermoplastic polyurethane elastomer according to claim any one of 1-4, it is characterised in that the polyethers is more
The number-average molecular weight of first alcohol is 1000-3000；
Preferably, the one kind of the PPG in polytetrahydrofuran diol, polyoxypropyleneglycol or polyethylene glycol
Or at least two combination；
Preferably, the PPG includes at least 60wt% polyoxypropyleneglycol；
Preferably, the PPG is by 60-80wt% polyoxypropyleneglycol and 20-40wt% PolyTHF two
Alcohol is constituted.
6. the transparent thermoplastic polyurethane elastomer according to claim any one of 1-5, it is characterised in that the chain extender
The small molecule alcohol of three-functionality-degree comprising 20-30wt%；
Preferably, the chain extender also includes 70-80wt% small molecule glycol；
Preferably, the small molecule alcohol of the three-functionality-degree is trimethylolpropane；
Preferably, the small molecule glycol is selected from ethylene glycol, BDO or one kind in 1,6- hexylene glycol or at least two
Combination.
7. the transparent thermoplastic polyurethane elastomer according to claim any one of 1-6, it is characterised in that the catalyst
One kind or at least two combination in organotin, organo-bismuth, Organic leadP or amines catalyst；
Preferably, the catalyst is organotin catalysts；
Preferably, the organotin catalysts are dibutyl tin laurate and/or stannous octoate.
8. the transparent thermoplastic polyurethane method for producing elastomers according to claim any one of 1-7, it is characterised in that
The preparation method comprises the following steps：
(1) diisocyanate, PPG and catalyst of formula ratio are mixed, reaction obtains base polyurethane prepolymer for use as；
(2) base polyurethane prepolymer for use as is mixed with the chain extender of formula ratio, stands reaction, obtain the poly- ammonia of the transparent thermoplastic
Ester elastomer.
9. preparation method according to claim 8, it is characterised in that the preparation method is additionally included in before step (1)
Processing is dried to the diisocyanate, PPG and chain extender；
Preferably, reaction is to carry out under agitation described in step (1)；
Preferably, the rotating speed of the stirring is 150-300r/min；
Preferably, the temperature reacted described in step (1) is 70-100 DEG C, and the time of the reaction is 0.5-2h；
Preferably, step (1) is additionally included in progress deaeration processing after reaction terminates；
Preferably, mixing is to carry out under agitation described in step (2)；
Preferably, the rotating speed of the stirring is 200-300r/min, and the time of the stirring is 10-20s；
Preferably, the temperature reacted described in step (2) is 90-120 DEG C, and the time of the reaction is 1-3h.
10. preparation method according to claim 8 or claim 9, it is characterised in that the preparation method comprises the following steps：
(1) processing is dried to the diisocyanate, PPG and chain extender；
(2) diisocyanate, PPG and catalyst of dry formula ratio are mixed, keeping temperature is 70-100 DEG C,
Under 150-300r/min rotating speed base polyurethane prepolymer for use as is obtained after stirring reaction 0.5-2h, deaeration；
(3) chain extender of the formula ratio by the base polyurethane prepolymer for use as with drying is stirred under 200-300r/min rotating speed mixes
10-20s, reaction 0.5-2h is stood at 90-120 DEG C, the transparent thermoplastic polyurethane elastomer is obtained.
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| CN111393606A (en) * | 2020-04-20 | 2020-07-10 | 上海应用技术大学 | High-transparency antibacterial thermoplastic polyurethane elastomer and preparation method thereof |
| CN111393607A (en) * | 2020-05-07 | 2020-07-10 | 江苏铁锚玻璃股份有限公司 | Formula of thermoplastic polyurethane elastomer rubber sheet and extrusion molding method thereof |
| WO2022062245A1 (en) * | 2020-09-22 | 2022-03-31 | 何建雄 | High transparent tpu film for electronic products and preparation method therefor |
| CN113045725A (en) * | 2021-04-08 | 2021-06-29 | 东莞市米儿塑胶原料有限公司 | Preparation method of antifogging TPU material and preparation method of film |
| CN114456347A (en) * | 2022-02-28 | 2022-05-10 | 赢聚化学技术研发(南京)有限公司 | Preparation method of anti-slip polyurethane sole transparent sole attaching material |
| CN114853977A (en) * | 2022-04-27 | 2022-08-05 | 盛鼎高新材料有限公司 | High-permeability high-elasticity polyurethane elastomer and preparation method thereof |
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