CN108084391A - A kind of polyurethane and preparation method thereof - Google Patents
A kind of polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN108084391A CN108084391A CN201611042586.3A CN201611042586A CN108084391A CN 108084391 A CN108084391 A CN 108084391A CN 201611042586 A CN201611042586 A CN 201611042586A CN 108084391 A CN108084391 A CN 108084391A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- polyester
- small
- diol
- isosorbide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 13
- -1 alcohol small molecule Chemical class 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 238000007039 two-step reaction Methods 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 229920003225 polyurethane elastomer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008876 conformational transition Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of polyurethane and preparation method thereof, and the soft segment of the polyurethane is obtained by the polyester-diol of the Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic of amorphous, is comprised the following steps：(1) polyester-diol of 1,4 cyclohexane cyclohexanedimethanodibasics of the molecular weight of amorphous controllably is prepared using 1,4 cyclohexane cyclohexanedimethanodibasics and ethylene glycol progress polycondensation reaction；(2) 1, the polyester-diol of 4 cyclohexane cyclohexanedimethanodibasics is as soft segment, prepare the polyurethane that soft segment main chain contains cyclohexane group, the method of the present invention is simple pollution-free, easy to implement and controls, production efficiency is higher, equipment is simple, and raw material is cheap, abundance, and cyclohexane group is introduced in the polyurethane so that its intensity is high, elasticity is good, the association areas such as chemical industry, machinery are can be widely applied to, there is important application value and good development prospect.
Description
Technical field
The present invention provides a kind of polyurethane and preparation method thereof, and in particular to a kind of poly- based on Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic
Urethane and preparation method.
Background technology
Polyurethane is a kind of high-molecular compound for containing multiple amino-formate bonds (- NH-COO-) in molecular backbone.It
Mainly formed by isocyanates and polyol by progressively polyaddition reaction.The special design feature of polyurethane is just
It is its more block structure, is become apparent from the polyurethane that this structure is synthesized in prepolymer method.By changing polyurethane preparation process
In raw materials used species and composition, can greatly adjust the form and performance of final products, produce including it is soft,
The different types of production such as semi-rigid and rigid foam, coating, adhesive, elastomer, elastomer and bio-medical material
Product.Wherein, for polyurethane elastomer material, soft segment is usually the polyester or polyethers of lower glass transition temperatures, strand
Submissiveer, elasticity is preferable, but flexible polyester or pfpe molecule limits the intensity of polyurethane, reduces elastic polyurethane
The comprehensive performance of body.Therefore, a kind of existing rigidity is designed, and has both the flexible polyurethane segment molecule chain of elasticity, can not only be carried
The soft segment glass transition temperature of high polyurethane, and on the basis of higher elasticity is kept improve polyurethane intensity.
Contain cyclohexane group in Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic strand, be a kind of rigidity and the standby binary acid list of elasticity
Body, polyester material and its preparation containing Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic structural unit have relevant report, for example, US6,084,055,
US4,327,206, CN200580014885.X etc., Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic structural unit is introduced into polyester material, is carried
The high intensity of polyester material, but be still a kind of plastics material since the polyester material prepared using such method is crystallization
Material, elastic property still cannot meet the needs, and using such method prepare polyurethane equally also can there are it is identical the problem of,
Therefore, the polyurethane that rigidity and elasticity are taken into account how is prepared to be a problem to be solved.
The content of the invention
In view of deficiency of the prior art, it is an object of the invention to provide a kind of polyurethane, and in particular to one kind is based on
The polyurethane of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, polyurethane material provided by the present invention is i.e. with higher intensity simultaneously again with excellent
Different elasticity.
The technical solution of the present invention：
A kind of polyurethane, the soft segment of the polyurethane are obtained by the polyester-diol of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic of amorphous, institute
The polyester-diol for stating Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is made by Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic with ethylene glycol by polycondensation reaction, and described
The cis-content of 1,4 cyclohexanedicarboxylic acid is 30%~70%.
The molar ratio of the 1,4 cyclohexanedicarboxylic acid and ethylene glycol is 1:1.2~1:2.
The condition of the polycondensation reaction is：When polycondensation reaction 1~5 is small under conditions of 180~195 DEG C and 90~180Pa.
The present invention also provides a kind of preparation methods of polyurethane, are realized by following steps：
(1) Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and ethylene glycol are added in polymeric kettle by a certain percentage, led at 80~100 DEG C
Enter nitrogen, and add in catalyst, reacted at 130~160 DEG C 3~5 it is small when, then heat and vacuumize, finally 180~
When polycondensation reaction 1~5 is small under conditions of 195 DEG C and 90~180Pa, the poly- of the controllable Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic of molecular weight is obtained
Esterdiol；
(2) polyester-diol of a certain proportion of 1,4 cyclohexanedicarboxylic acid is made with diisocyanate by two-step reaction
The polyurethane.
The cis-content of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 30%~70% in the step (1), by controlling cis-content,
Its object is to be more easy to obtain the product of amorphous, highly crystalline product is easy to get if trans content is too high；
The molar ratio of 1,4 cyclohexanedicarboxylic acid and ethylene glycol is preferably 1 in the step (1):1.2~1:2, reaction
Ethylene glycol is excessive in the process, it is therefore intended that, it is ensured that ethylene glycol blocks Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, if ethylene glycol too much if
Bad removal, loses time and resource, in addition, the present invention selects ethylene glycol to react with Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, is more easy to obtain
Amorphous product；
Catalyst is Titanium series catalyst in the step (1), preferably, the catalyst is butyl titanate；
The polyester-diol of 1,4 cyclohexanedicarboxylic acid and diisocyanate molar ratio are preferably 1 in the step (2):2
~1:10, it not only can guarantee the high intensity of polyurethane within this range but also can guarantee the high resiliency of polyurethane；
Diisocyanate is the diisocyanate of aromatics in the step (2), preferably, the diisocyanate
For one kind in diphenyl methane -4,4 '-diisocyanate, toluene di-isocyanate(TDI)；
In the step (2), the two-step reaction of polyurethane is prepared as the ordinary skill in the art, two step of the invention
Reaction condition control is as follows：The polyester-diol of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and diisocyanate are added in polar solvent,
When reaction 2~4 is small at 40~60 DEG C, catalyst then is added at 60 DEG C~70 DEG C, and adds in small point of a certain amount of dihydric alcohol
Son is used as chain extender, when reaction 2~5 is small.
Further, catalyst is tertiary amine or organotin in the step (2), preferably, the catalyst is two
Dibutyl tin laurate catalyst；
Glycol chain extender is one kind in 1,4- butanediols, hexylene glycol, 1,4 cyclohexane dimethanol in the step (2)
Or more than one mixture, preferably, the glycol chain extender is 1,4-butanediol, the glycol chain extender
Molar content for diisocyanate molar content and 1,4 cyclohexanedicarboxylic acid polyester-diol molar content difference.
Polar solvent in the step (2) is to prepare the soft segment of polyurethane and the common reaction dissolvent of hard section, preferably N,
Dinethylformamide；
Preferably, the weight content of soft segment is 50%~70% in the polyurethane prepared in the step (2).
The present invention is compared with the characteristics of the prior art and advantage：
The present invention selects polyethylene glycol and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic reaction first, and controls Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic
Cis-content obtains the polyester-diol of amorphous, go forward side by side a step control polycondensation reaction time and reaction pressure so that the polyester of amorphous
Glycol molecular weight is controllable, convenient for subsequently accurately controlling its rate of charge, regulates and controls the ratio of hard section and soft segment, and secondly, the present invention will
Soft segment of the amorphous polyester glycol of preparation as polyurethane further obtains the polyurethane elastomer of amorphous, and in the polyurethane
Cyclohexane group is introduced, cyclohexane group is a kind of on-plane surface six-membered ring structure, bigger than linear aliphatic chain structural rigidity, and six
The conformation transition of yuan of rings ship-structure of chair causes it to have preferable elasticity, is introduced into polyurethane, can improve polyurethane
The comprehensive performance of elastomer so that the intensity and elasticity of polyurethane elastomer have both.The preparation method of the present invention is simple, it is real to be easy to
Apply and control, production efficiency is higher, equipment is simple, and raw material is cheap, abundance, contains hexamethylene in the polyurethane backbone of preparation
Groups, the intensity of elastomeric material is high, and elasticity is good, can be widely applied to the association areas such as chemical industry, machinery, has important answer
With value and good development prospect.
Description of the drawings
Fig. 1 is the reaction scheme figure that 1,4 cyclohexanedicarboxylic acid prepares polyester-diol with ethylene glycol
Fig. 2 be poly- 1,4 cyclohexanedicarboxylic acid glycol ester embodiment nucleus magnetic hydrogen spectrum (1HNMR schemes)
Fig. 3 is the polyurethane embodiment that soft segment is poly- 1,4 cyclohexanedicarboxylic acid glycol ester1HNMR schemes
Specific embodiment
Nuclear magnetic resonance spectroscopy in embodiment1HNMR uses the III type spectroscopes of 400AVANCE of Brooker company (Bruker)
(Spectrometer) measure, 400MHz, solvent is deuterochloroform and deuterated dimethyl sulfoxide；Mechanical stretch is used according to standard
Polyurethane film is cut into IV type dumbbell shaped battens by GB/T 528-2009, and long 35mm, wide 2mm, thickness is about 0.5mm, is carried out
Tensile property is tested.Test equipment is Instron5567 type universal testing machines, and tensile speed 100mm/min, temperature is
25℃.Each sample test 5 times, takes its average value.
Embodiment 1
In the reaction kettle of 500mL, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic (cis molar content is 70%) of 100g is separately added into,
72g ethylene glycol, at 90 DEG C pump drainage three times, and be passed through nitrogen protection, add in 2 drop butyl titanates as catalyst, exist respectively
At 130 DEG C, 145 DEG C and 160 DEG C reaction 1 it is small when, 1 it is small when and 2 it is small when.It is to be esterified completely after, taken out at 160 DEG C using oil pump true
When sky 1 is small, vacuum degree is made to reach 300Pa.Then at 180 DEG C using oil pump vacuumize 1 it is small when, vacuum degree reaches 180Pa.It will
It after reaction product is dissolved with chloroform, pours into methanol and is precipitated, the volume ratio of chloroform and methanol is less than 1:4.Such as
This cycle three times, finally product is placed at 50 DEG C of vacuum drying oven 24 it is small when, remove remaining solvent, obtain polyester-diol
(poly- 1,4 cyclohexanedicarboxylic acid glycol ester).It utilizes1The molecular weight that HNMR measures the polyester-diol is 2100g/mol.
Embodiment 2
In the reaction kettle of 500mL, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic (cis molar content is 70%) of 100g is separately added into,
72g ethylene glycol, at 90 DEG C pump drainage three times, and be passed through nitrogen protection, add in 2 drop butyl titanates as catalyst, exist respectively
At 130 DEG C, 145 DEG C and 160 DEG C reaction 1 it is small when, 1 it is small when and 2 it is small when.It is to be esterified completely after, taken out at 160 DEG C using oil pump true
When sky 1 is small, vacuum degree is made to reach 300Pa.Then at 180 DEG C using oil pump vacuumize 2 it is small when, vacuum degree reaches 120Pa.It will
It after reaction product is dissolved with chloroform, pours into methanol and is precipitated, the volume ratio of chloroform and methanol is less than 1:4.Such as
This cycle three times, finally product is placed at 50 DEG C of vacuum drying oven 24 it is small when, remove remaining solvent, obtain polyester-diol
(poly- 1,4 cyclohexanedicarboxylic acid glycol ester).It utilizes1The molecular weight that HNMR measures the polyester-diol is 3200g/mol.
Embodiment 3
In the reaction kettle of 500mL, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic (cis molar content is 70%) of 100g is separately added into,
72g ethylene glycol, at 90 DEG C pump drainage three times, and be passed through nitrogen protection, add in 2 drop butyl titanates as catalyst, exist respectively
At 130 DEG C, 145 DEG C and 160 DEG C reaction 1 it is small when, 1 it is small when and 2 it is small when.It is to be esterified completely after, taken out at 160 DEG C using oil pump true
When sky 1 is small, vacuum degree is made to reach 300Pa.Then at 180 DEG C using oil pump vacuumize 3 it is small when, vacuum degree reaches 90Pa.It will
It after reaction product is dissolved with chloroform, pours into methanol and is precipitated, the volume ratio of chloroform and methanol is less than 1:4.Such as
This cycle three times, finally product is placed at 50 DEG C of vacuum drying oven 24 it is small when, remove remaining solvent, obtain polyester-diol
(poly- 1,4 cyclohexanedicarboxylic acid glycol ester).It utilizes1The molecular weight that HNMR measures the polyester-diol is 4600g/mol.
Above-mentioned 3 embodiments are to prepare the embodiment of the polyester-diol based on Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, Isosorbide-5-Nitrae-hexamethylene
The reaction scheme figure that dioctyl phthalate prepares polyester-diol with ethylene glycol is shown in Fig. 1, as representative, poly- Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic ethylene glycol
Ester (molecular weight 3200g/mol)1HNMR figures are shown in Fig. 2.
Embodiment 4
The poly- 1,4 cyclohexanedicarboxylic acid glycol ester that 15g molecular weight is 2100g/mol is added to three mouthfuls of burnings of 250mL
In bottle, when utilizing vacuum oil pumping 1 small at 100 DEG C, nitrogen protection is passed through, and is cooled to 45 DEG C.Then add in there-necked flask
Enter the DMF (n,N-Dimethylformamide) of diphenyl methane -4 of 8g, 4 '-diisocyanate and 30g dryings, when reaction 3 is small.
The content of-NCO in above-mentioned system, the 1,4-butanediol of the amount 1/2 of addition-NCO substances are measured, and adds in 2 drops two
Dibutyl tin laurate catalyst, be warming up to 60 DEG C the reaction was continued 3 it is small when.Above-mentioned reactant is added in methanol, makes product
It is precipitated, filters out product, be dissolved in appropriate n,N-Dimethylformamide, solution is poured into mold, drying and moulding is gathered
Urethane film.
Embodiment 5
The poly- 1,4 cyclohexanedicarboxylic acid glycol ester that 15g molecular weight is 3200g/mol is added to three mouthfuls of burnings of 250mL
In bottle, when utilizing vacuum oil pumping 1 small at 100 DEG C, nitrogen protection is passed through, and is cooled to 45 DEG C.Then add in there-necked flask
Enter the DMF (n,N-Dimethylformamide) of diphenyl methane -4 of 7.8g, 4 '-diisocyanate and 30g dryings, when reaction 3 is small.
The content of-NCO in above-mentioned system, the 1,4-butanediol of the amount 1/2 of addition-NCO substances are measured, and adds in 2 drops two
Dibutyl tin laurate catalyst, be warming up to 60 DEG C the reaction was continued 3 it is small when.Above-mentioned reactant is added in methanol, makes product
It is precipitated, filters out product, be dissolved in appropriate n,N-Dimethylformamide, solution is poured into mold, drying and moulding is gathered
Urethane film.
Embodiment 6
The poly- 1,4 cyclohexanedicarboxylic acid glycol ester that 15g molecular weight is 4600g/mol is added to three mouthfuls of burnings of 250mL
In bottle, when utilizing vacuum oil pumping 1 small at 100 DEG C, nitrogen protection is passed through, and is cooled to 45 DEG C.Then add in there-necked flask
Enter the DMF (n,N-Dimethylformamide) of diphenyl methane -4 of 7.5g, 4 '-diisocyanate and 30g dryings, when reaction 3 is small.
The content of-NCO in above-mentioned system, the 1,4-butanediol of the amount 1/2 of addition-NCO substances are measured, and adds in 2 drops two
Dibutyl tin laurate catalyst, be warming up to 60 DEG C the reaction was continued 3 it is small when.Above-mentioned reactant is added in methanol, makes product
It is precipitated, filters out product, be dissolved in appropriate n,N-Dimethylformamide, solution is poured into mold, drying and moulding is gathered
Urethane film.
Above-mentioned 3 embodiments are to prepare the embodiment of the polyurethane based on Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, as representative, soft segment
For the polyurethane of poly- 1,4 cyclohexanedicarboxylic acid glycol ester (molecular weight 3200g/mol)1HNMR figures are shown in Fig. 3.
As representative, mechanical property is as shown in table 1 at room temperature for prepared polyurethane elastomer in embodiment 5.
1. polyurethane mechanical performance data of table
As it can be seen from table 1 its elongation at break of polyurethane prepared by the present invention, more than 500%, (stretching should for response rate
Become 250%) being more than 88%, illustrate its elasticity preferably；And its tensile strength is more than 24MPa, stretch modulus is more than 110MPa, greatly
Exceed the tensile strength and elasticity modulus of polyurethane of the prior art greatly, intensity is greatly improved, i.e., institute of the present invention
The polyurethane of preparation takes into account excellent intensity and elastic property.
Above-mentioned is to elaborate in conjunction with the embodiments to the present invention, but embodiments of the present invention and from above-mentioned implementation
Simplified etc. be included in is combined in the limitation of example, other any changes made under patent core guiding theory of the present invention, replacement
Within the protection domain of patent of the present invention.
Claims (8)
1. a kind of polyurethane, it is characterised in that：The soft segment of the polyurethane by amorphous 1,4 cyclohexanedicarboxylic acid polyester two
Alcohol obtains, and the polyester-diol of the Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic passes through polycondensation reaction system by Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and ethylene glycol
, and the cis-content of the Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 30%~70%.
2. a kind of polyurethane according to claim 1, it is characterised in that：The 1,4 cyclohexanedicarboxylic acid and ethylene glycol
Molar ratio is 1:1.2~1:2.
3. a kind of polyurethane according to claim 1, which is characterized in that the condition of the polycondensation reaction is：180~
When polycondensation reaction 1~5 is small under conditions of 195 DEG C and 90~180Pa.
4. a kind of preparation method of polyurethane, which is characterized in that realized by following steps：
(1) Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and ethylene glycol are added in polymeric kettle by a certain percentage, nitrogen is passed through at 80~100 DEG C
Gas, and catalyst is added in, when reaction 3~5 is small at 130~160 DEG C, then heats and vacuumize, finally at 180~195 DEG C
With polycondensation reaction under conditions of 90~180Pa 1~5 it is small when, obtain the polyester two of the controllable Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic of molecular weight
Alcohol；
(2) polyester-diol of a certain proportion of 1,4 cyclohexanedicarboxylic acid and diisocyanate are made described by two-step reaction
Polyurethane.
5. according to the method described in claim 4, it is characterized in that：The molar ratio of the 1,4 cyclohexanedicarboxylic acid and ethylene glycol
Example is preferably 1:1.2~1:2.
6. according to the method described in claim 4, it is characterized in that：The cis-content of the 1,4 cyclohexanedicarboxylic acid is 30%
~70%.
7. according to the method described in claim 4-6, it is characterised in that：The polyester-diol of the 1,4 cyclohexanedicarboxylic acid and two
Isocyanates molar ratio is preferably 1:2~1:10.
8. according to the method described in claim 4-7, which is characterized in that step (2) specific embodiment is as follows：By 1,4-
The polyester-diol of cyclohexane cyclohexanedimethanodibasic is added to diisocyanate in polar solvent, when reaction 2~4 is small at 40~60 DEG C,
Then catalyst is added at 60 DEG C~70 DEG C, and adds in a certain amount of dihydric alcohol small molecule as chain extender, reaction 2~5 is small
When.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611042586.3A CN108084391A (en) | 2016-11-21 | 2016-11-21 | A kind of polyurethane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611042586.3A CN108084391A (en) | 2016-11-21 | 2016-11-21 | A kind of polyurethane and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108084391A true CN108084391A (en) | 2018-05-29 |
Family
ID=62171010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611042586.3A Pending CN108084391A (en) | 2016-11-21 | 2016-11-21 | A kind of polyurethane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108084391A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940221A (en) * | 2021-04-26 | 2021-06-11 | 浙江华峰合成树脂有限公司 | Polyurethane resin of soft synthetic leather for clothes and preparation method thereof |
| CN116179012A (en) * | 2022-12-23 | 2023-05-30 | 杭州柏盛印刷有限公司 | Water-based UV (ultraviolet) ink and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352924A (en) * | 1981-06-29 | 1982-10-05 | Eastman Kodak Company | Thermosetting powder coating compositions |
| JPS63288747A (en) * | 1987-05-21 | 1988-11-25 | Toyobo Co Ltd | Thermoplastic resin laminated film |
| JPH03192738A (en) * | 1989-12-21 | 1991-08-22 | Tanaka Denshi Kogyo Kk | Resin-covered bonding wire |
| JPH0431422A (en) * | 1990-05-25 | 1992-02-03 | Dainippon Ink & Chem Inc | Actinic radiation curable resin composition |
| CN1456620A (en) * | 2002-05-10 | 2003-11-19 | 德古萨公司 | Modified polyester powder coating based on polyester and thermosetting material |
| CN101210151A (en) * | 2006-12-29 | 2008-07-02 | 德古萨有限责任公司 | Method for coating metal strip |
| JP2010235811A (en) * | 2009-03-31 | 2010-10-21 | Kuraray Co Ltd | Alicyclic polyester polyol and method for producing the same |
| CN102234369A (en) * | 2010-04-20 | 2011-11-09 | 日本碧化学公司 | Polyester resin and purposes thereof |
| CN105622906A (en) * | 2014-11-03 | 2016-06-01 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic polyester elastomer and preparation method and application thereof |
| CN105802196A (en) * | 2016-02-19 | 2016-07-27 | 中山大学 | High polymer material with two-way shape memory effect and preparation method thereof |
-
2016
- 2016-11-21 CN CN201611042586.3A patent/CN108084391A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352924A (en) * | 1981-06-29 | 1982-10-05 | Eastman Kodak Company | Thermosetting powder coating compositions |
| JPS63288747A (en) * | 1987-05-21 | 1988-11-25 | Toyobo Co Ltd | Thermoplastic resin laminated film |
| JPH03192738A (en) * | 1989-12-21 | 1991-08-22 | Tanaka Denshi Kogyo Kk | Resin-covered bonding wire |
| JPH0431422A (en) * | 1990-05-25 | 1992-02-03 | Dainippon Ink & Chem Inc | Actinic radiation curable resin composition |
| CN1456620A (en) * | 2002-05-10 | 2003-11-19 | 德古萨公司 | Modified polyester powder coating based on polyester and thermosetting material |
| CN101210151A (en) * | 2006-12-29 | 2008-07-02 | 德古萨有限责任公司 | Method for coating metal strip |
| JP2010235811A (en) * | 2009-03-31 | 2010-10-21 | Kuraray Co Ltd | Alicyclic polyester polyol and method for producing the same |
| CN102234369A (en) * | 2010-04-20 | 2011-11-09 | 日本碧化学公司 | Polyester resin and purposes thereof |
| CN105622906A (en) * | 2014-11-03 | 2016-06-01 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic polyester elastomer and preparation method and application thereof |
| CN105802196A (en) * | 2016-02-19 | 2016-07-27 | 中山大学 | High polymer material with two-way shape memory effect and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| A. H. JOHNSON等: "Hydrolytic stability of oligoesters: comparison of steric with anchimeric effects", 《EUROPEAN POLYMER JOURNAL》 * |
| HAI NI等: "Cycloaliphatic Polyester Based High Solids Polyurethane Coatings:Ⅰ.The Effect of Difunctional Alcohols", 《JOURNAL OF COATING TECHNOLOGY》 * |
| MAYELA RAMIREZ-HUERTA等: "Phenyl carbamate end-capped oligoesters: a model for hydrolytic stability of ester-based urethanes", 《JOURNAL OF COATINGS TECHNOLOGY AND RESEARCH》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940221A (en) * | 2021-04-26 | 2021-06-11 | 浙江华峰合成树脂有限公司 | Polyurethane resin of soft synthetic leather for clothes and preparation method thereof |
| CN116179012A (en) * | 2022-12-23 | 2023-05-30 | 杭州柏盛印刷有限公司 | Water-based UV (ultraviolet) ink and preparation method thereof |
| CN116179012B (en) * | 2022-12-23 | 2023-10-20 | 杭州柏盛印刷有限公司 | Water-based UV (ultraviolet) ink and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111217985B (en) | Metal coordination self-healing polyurethane elastomer and preparation method thereof | |
| Kojio et al. | Structure− mechanical property relationships for poly (carbonate urethane) elastomers with novel soft segments | |
| CN110885550B (en) | Organic silicon modified thermoplastic polyurethane elastomer and preparation method thereof | |
| CN102604038B (en) | Transparent polyurethane elastomer and preparation method as well as application | |
| van der Schuur et al. | Polyurethane elastomers with amide chain extenders of uniform length | |
| CN108503783B (en) | Thermoplastic polyurethane elastomer and preparation method thereof | |
| CN113831493B (en) | Self-repairing polyurethane elastomer containing six-fold intermolecular hydrogen bonds and preparation method thereof | |
| CN107266658B (en) | Polyurethane elastomer with main chain containing ferrocene and preparation method thereof | |
| CN101717485A (en) | Method for preparing high-toughness thermoplastic fluorine-containing polyurethane elastomer | |
| CN110204681B (en) | Preparation method of self-healing fluorescent polyurethane film containing imidazolidinyl urea at hard segment | |
| WO1994025529A1 (en) | Thermoplastic polyurethane composition | |
| CN110627985A (en) | Polylactic acid-based thermoplastic polyurethane elastomer material and preparation method thereof | |
| JPWO2011125540A1 (en) | Thermoplastic polyurethane resins and molded products | |
| JP2020512430A (en) | A process for producing polyurethanes exhibiting low blooming effect and good low temperature flexibility based on urethane-containing polymeric hydroxyl compounds. | |
| CN104448231A (en) | Method for manufacturing polyether organosilicone segmented polyurethane material, product and application | |
| CN108484868B (en) | Self-healing material based on polyurethane and preparation method thereof | |
| CN115181232A (en) | Polyurethane material and preparation method and application thereof | |
| CN108084391A (en) | A kind of polyurethane and preparation method thereof | |
| CN113956522B (en) | Preparation method of high-strength polyurethane product | |
| CN109322008B (en) | Method for improving performance stability of spandex product | |
| CN109575233B (en) | Polysiloxane polyether type polyurethane elastomer with high mechanical property and preparation method thereof | |
| CN113136017B (en) | Polyurethane with pH response and self-healing performance and preparation method thereof | |
| CN105294970A (en) | Bio-based thermoplastic polyurethane elastomer material and preparation method thereof | |
| JP5386142B2 (en) | Polyurethane elastomers and molded products | |
| PT97089A (en) | PROCESS FOR THE PREPARATION OF POLIOXYALKYLENE-POLYOLES CONTAINING INTERNAL BLOCKS OF POLYOXYETHYLENE AND POLYURETHANES OBTAINED THEREOF |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180529 |
|
| WD01 | Invention patent application deemed withdrawn after publication |