CN100460437C - Synthesis method of high-performance multipurpose urethane elastomer - Google Patents

Synthesis method of high-performance multipurpose urethane elastomer Download PDF

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CN100460437C
CN100460437C CNB2006100892377A CN200610089237A CN100460437C CN 100460437 C CN100460437 C CN 100460437C CN B2006100892377 A CNB2006100892377 A CN B2006100892377A CN 200610089237 A CN200610089237 A CN 200610089237A CN 100460437 C CN100460437 C CN 100460437C
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weight
performance multipurpose
synthesis method
rubber
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CN1919890A (en
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于晶
胡少坤
张凤英
齐永新
潘广勤
胡开放
陈继明
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China National Petroleum Corp
Petrochina Lanzhou Petrochemical Co
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Petrochina Lanzhou Petrochemical Co
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Abstract

The invention discloses a synthetic method to prepare polyurethane elastic body with hydroxyl-ended oligomer polyol as raw material, which is characterized by the following: reacting hydroxy-terminated liquid rubber or poly-tetrahydropyran ether alcohol with polyisocyanates; getting end isocyanate group pie polymer in fixing reacting time, temperature; giving in A component; compositing chain-extending agent, flux, antiager with gallant; getting curative; giving in B component; hardening A component and B component under indoor temperature proportional mixing; getting high-performance multipurpose polyurethane elastic body; The stretching intensity is: 10.0-47.0Mpa, splitting extensibility>300%, 300% load at certain intensity: 5.0-35.0Mpa.

Description

Synthesis method of high-performance multipurpose urethane elastomer
Technical field
The present invention relates to a kind of is raw material with the terminal hydroxy group oligomer polyol, the preparation method for synthesizing urethane elastomer.With terminal hydroxy group class I liquid I rubber or polytetrahydrofuran ether alcohol, with the polyisocyanates reaction, under the reaction times of stipulating, temperature, make isocyanate terminated basic performed polymer, be the A component; Compound with chainextender, solvent, anti-aging agent and linking agent, obtain solidifying agent, be the B component; A component and B component are mixed in proportion at room temperature solidifies, and makes the high-performance multipurpose urethane elastomerics.
Background technology
At present, polyurethane elastomer is the polymer substance of the many blocks of a class, owing to contain hard section of strong polar carbamate formula in its macromolecular chain, contain soft section of flexible fabulous polyester formula or polyethers formula again, it is become not only be rich in intensity but also rubber-like thermoplastic elastomer; One of it is that a class all has good cementability to most of metals or non-metallic material, and the sizing material that has been used widely.Its outstanding feature is that bonding force is strong, corrosion-resistant, wear resistance, oil-proofness and ozone resistance brilliance, and low-temperature performance is also very outstanding.And high-performance polyurethane elastomer not only has the performance of general polyurethane, also have such as resistance to hydrolysis, cold flexibility, antimicrobial and mould characteristic, high resilience, electrical insulating property, higher characteristic such as shaping performance under good cryogenic mechanics performance, the normal temperature, and these characteristics, make the more areas of high-performance polyurethane elastomer in national economy, especially special dimension is as sealing material, electrically insulating material, electronic encapsulation material etc. have good application prospect.
Diolefine type polyurethane elastomerics is one of principal item of high-performance polyurethane elastomer, and it comprises two kinds of multipolymer (HTBN) fluid rubbers of hydroxy-terminated polybutadienes (HTPB) fluid rubber and divinyl and vinyl cyanide.Diolefine type polyurethane elastomer performance is good, and variable range is big, and its contained hydroxyl reaction is active high, at room-temperature-curable, during curing heat release few, do not have shrinkage phenomenon substantially.Its electrical insulation capability excellence, the volume resistance height.Because of not ether-containing key and ester bond in the molecular skeleton of HTPB and HTBN, so resistance to hydrolysis can be excellent, and preservative property are good, and resistance to low temperature and acid-proof alkaline are outstanding.This class polyurethane elastomer second-order transition temperature Tg is below-70 ℃, and wherein HTBN is owing to the introducing of vinyl cyanide, and its product oil-proofness is better.At present, China is applied in the war industrys such as solid propellant and lining maturely.Because the singularity of China's military industry, and reason such as the fluid rubber price is higher, and manufacturer is single, thereby limited it at civil area, as electrically insulating material, widespread uses such as electronic encapsulation material.
Polyether glycol or polyester polyol class have the amino of containing owing to promptly contain carbonyl in the structure, can interact with many polar groups, form hydrogen bond etc., therefore has extremely excellent absorption bonding force, have snappiness, wear resistance and higher breaking tenacity concurrently, thereby be widely used in fields such as timber, electronic apparatus, automobile making.At present, synthetic PTMG or the hydroxy-terminated polybutadienes or butyronitrile hydroxyls (HTBN) of adopting of isocyanate terminated basic performed polymer more, N, N dihydroxypropyl aniline (BHPA) is raw material, with tolylene diisocyanate (TDI) or poly methylene poly phenyl poly isocyanate (PAPI) or 4,4,-diphenylmethanediisocyanate (MDI) or 1, the synthetic isocyanate terminated performed polymer of 5-naphthalene diisocyanate (NDI) reaction, be the solidifying agent sulfidization molding with aromatic diamine MOCA or by diphenylmethanediisocyanate liquid with the solidifying agent that comprises PTMG etc. again, obtain polyurethane elastomer.Be mainly used in fields such as timber, electronic apparatus, automobile making
Summary of the invention
The purpose of this invention is to provide a kind of synthesis method of high-performance multipurpose urethane elastomer, make the elastomeric production technique of synthesis of polyurethane more become reasonable; Acquisition quality product height, good combination property.Adjust, select the different material prescription for use, obtain the different polyurethane elastomer of performance.
The technical solution used in the present invention is:
Synthesis method of high-performance multipurpose urethane elastomer is: with terminal hydroxy group class I liquid I rubber or polytetrahydrofuran ether alcohol, with the polyisocyanates reaction, make isocyanate terminated basic performed polymer under the reaction times of stipulating, temperature, be the A component; Compound with chainextender, solvent, anti-aging agent and linking agent, obtain solidifying agent, be the B component; A component and B component are mixed in proportion at room temperature solidifies, and makes the high-performance multipurpose urethane elastomerics.
In the elastomeric building-up process of high-performance multipurpose urethane, described A component and B components by weight between 1.0-6.0:1, mixing and stirring.Condition of cure is: room temperature, the solidified time is between 80-100 hours.
In high-performance multipurpose urethane elastomerics synthesis material, described terminal hydroxy liquid rubber is a kind of in terminal hydroxy polybutadiene liquid rubber or the hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber, wherein: the molecular-weight average of terminal hydroxy polybutadiene liquid rubber is 3000-4000, average functionality 2-4, hydroxyl value is at 0.4-0.9mmol/g; The molecular-weight average of hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber is 2000-3500, average functionality 2-4, and itrile group binding capacity 14-25%, hydroxyl value is at 0.4-0.7mmol/g.The molecular-weight average of described polytetrahydrofuran ether alcohol is between 800-1500, and average functionality is between 2-4, and hydroxyl value is between 1.3-1.9mmol/g.
In high-performance multipurpose urethane elastomerics synthesis material, polyisocyanates comprises tolylene diisocyanate (TDI), 4,4,-diphenylmethanediisocyanate (MDI), 1, a kind of in 5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI) or the PPDI (PPDI).
Synthesis method of high-performance multipurpose urethane elastomer, the formulation weight ratio of preparation A component: the weight of terminal hydroxy group class I liquid I rubber or PTMG alcoholic solution is between 60-90%, and the weight of polyisocyanates is between 10-40%; Polymerizing condition: temperature was reacted 0.5-1 hour between 85-95 ℃, was cooled to 70-85 ℃ of isothermal reactions 2.5-5.0 hours, and NCO% is between 2-20% in the synthetic performed polymer that obtains.
Synthesis method of high-performance multipurpose urethane elastomer, the compound preparation B of described chainextender, solvent, anti-aging agent and linking agent component, the condition of its compound preparation is: under room temperature, the normal pressure, described material mixing and stirring is got final product.
Preparation B component in the synthesis method of high-performance multipurpose urethane elastomer, described chainextender is N, N is two-derivative of 2-hydroxypropyl-aniline, its consumption with NCO in the mol ratio of OH in the chainextender and the isocyanate terminated basic performed polymer between 0.075-0.11.
Described linking agent is 3,3 ,-two chloro-4,4, a kind of in-diamino-ditan or the 4-methyl-2.6-diaminostilbene, 3 benzene diformazan mercaptos, dosage of crosslinking agent with among NH2 in the linking agent and the component A-mol ratio of NCO is between 0.80-1.2;
Described anti-aging agent is 2,6 ditertiary butyl p cresol or 2, a kind of in 2-methylene double-basis-4-methyl-6-tert butyl-phenol, and the weight ratio of anti-aging agent component A is 0.1-0.15%;
Described solvent is organic alcohol or ketone, and wherein organic alcohol is dehydrated alcohol; Ketone comprises: acetone, 2-butanone, pimelinketone etc.; Solvent load is the 40-300% of linking agent weight.
Adopt the high-performance multipurpose urethane elastomerics of synthetic method preparation of the present invention, can be according to requirements of different users, select different material for use, do any adjustment, performed polymer mixes with composite curing agent, at room temperature solidifies, and the polyurethane elastomer tensile strength of acquisition is: 10.0-47.0MPa, elongation at break〉300%, 300% tensile modulus is: 5-35.0MPa.
In order to obtain the multi-purpose polyurethane elastomer of multiple performance, preparation process can also adopt two kinds of different A components to mix with a kind of B component.
Beneficial effect of the present invention: the isocyanate terminated basic performed polymer of synthetic of the present invention is as the A component; Again with compound solidifying agent that obtains such as chainextender, solvent, anti-aging agent and linking agents as the B component; Performed polymer A component is mixed with composite curing agent B component, at room temperature mixing cured after, obtain the high-performance multipurpose urethane elastomerics.Its tensile strength: 10.0-47.0MPa, elongation at break〉300%, 300% tensile modulus: 5.0-35.0MPa.The different material prescription be adjusted, be selected for use to the high-performance multipurpose urethane elastomerics can, the polyurethane elastomer that obtained performance is different according to user's different demands.More become rationally quality product height, good combination property by the elastomeric technology of synthesized high-performance multipurpose urethane of the present invention.
Embodiment
The terminal hydroxy polybutadiene liquid rubber that the present invention can select for use Lanzhou petrochemical corporation (complex) to produce: molecular weight 3689, hydroxyl value be at 0.5346mmol/g, viscosity 9.08Pa.s (40 ℃); Hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber that Lanzhou petrochemical corporation (complex) produces: molecular weight 2789, hydroxyl value are at 0.4806mmol/g, and nitrile group content is 16.09%, viscosity 50.32Pa.s (40 ℃); Polyether-tribasic alcohol is selected N-330 for use: molecular weight 3189, and hydroxyl value is at 0.5946mmol/g; PTMG is selected for use: molecular weight 890, hydroxyl value is at 1.5993mmol/g.
Embodiment 1
At first prepare performed polymer (component A): in the there-necked flask of 3 liters, add 1200 gram hydroxy-terminated polybutadienes-vinyl cyanide fluid rubbers.The molecular-weight average of hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber is 2789, average functionality 2.3, and itrile group binding capacity 16.09%, hydroxyl value is at 0.4806mmol/g.Be heated to 100 ± 5 ℃, vacuumize 30min, be cooled to 50 ℃ then, add tolylene diisocyanate 261 grams.The intensification polymerization temperature reacted 0.5 hour between 90 ℃, was cooled to 75 ℃, and isothermal reaction 4.5h vacuumizes 30min then, and obtaining the middle NCO% of isocyanate terminated basic butyronitrile fluid rubber performed polymer (component A) is 5.46, cooling discharge.
Preparation solidifying agent (B component): chainextender adopts N, and N is two-derivative of 2-hydroxypropyl-aniline, and its consumption is 0.1 calculating in NCO in the mol ratio of OH in the chainextender (OH is 6.74mmol/g, and is identical) and the isocyanate terminated basic performed polymer.Linking agent adopts 3,3 ,-two chloro-4,4 ,-diamino-ditan, its consumption among NH2 in the linking agent (NH2 is 7.5mmol/g, down with) and the component A-mol ratio of NCO is 0.89 calculating.Anti-aging agent adopts 2,6 ditertiary butyl p cresol.Aging inhibitor dosage is 0.1% of isocyanate terminated basic performed polymer (component A) weight ratio.Solvent adopts organic pure dehydrated alcohol, and consumption is 300% of a linking agent weight.
Make the high-performance multipurpose urethane elastomerics at last: A component and B components by weight are 1.8:1.Mixing and stirring, room temperature was solidified 90 hours.The high-performance multipurpose urethane elastomer product tensile strength that obtains: 13.11MPa, elongation at break 321%, 300% tensile modulus: 9.42MPa.
Embodiment 2
At first prepare performed polymer (component A): in the there-necked flask of 3 liters, add 1500 gram terminal hydroxy polybutadiene liquid rubber.The molecular-weight average of terminal hydroxy polybutadiene liquid rubber is 3715, average functionality 2.1, and hydroxyl value is at 0.4914mmol/g.Be heated to 102 ℃, vacuumize 50min, be cooled to 50 ℃ then, add tolylene diisocyanate 432 grams.The intensification polymerization temperature reacted 1 hour between 85 ℃, was cooled to 80 ℃, and isothermal reaction 3.5h vacuumizes 30min then, and obtaining the middle NCO% of isocyanate terminated basic butyronitrile fluid rubber performed polymer (component A) is 9.56, cooling discharge.
Preparation solidifying agent (B component): chainextender adopts N, and N is two-derivative of 2-hydroxypropyl-aniline, and its consumption is 0.095 with NCO in the mol ratio of OH in the chainextender and the isocyanate terminated basic performed polymer.Linking agent adopts 3,3 ,-two chloro-4,4 ,-diamino-ditan, dosage of crosslinking agent with among NH2 in the linking agent and the component A-mol ratio of NCO is between 0.9.Anti-aging agent adopts 2,6 ditertiary butyl p cresol.Aging inhibitor dosage is 0.13% of isocyanate terminated basic performed polymer (component A) weight ratio.Solvent adopts 2-butanone, and consumption is 100% of a linking agent weight.
Make the high-performance multipurpose urethane elastomerics at last: A component and B components by weight are 1.73:1.Mixing and stirring, room temperature was solidified 90 hours.The high-performance multipurpose urethane elastomer product tensile strength that obtains: 17.11MPa, elongation at break 339%, 300% tensile modulus: 10.37MPa.
Embodiment 3
At first prepare performed polymer (component A): in the there-necked flask of 3 liters, add 1300 gram PTMG.PTMG molecular-weight average 890, average functionality 2.9, hydroxyl value is at 1.5993mmol/g.Be heated to 105 ℃, vacuumize 50min, be cooled to 50 ℃ then, add tolylene diisocyanate 441 grams.The intensification polymerization temperature reacted 0.5 hour between 95 ℃, was cooled to 80 ℃, and isothermal reaction 2.5h vacuumizes 30min then, and obtaining the middle NCO% of isocyanate terminated basic butyronitrile fluid rubber performed polymer (component A) is 5.98, cooling discharge.
Preparation solidifying agent (B component): chainextender adopts N, and N is two-derivative of 2-hydroxypropyl-aniline, and its consumption is 0.1 with NCO in the mol ratio of OH in the chainextender and the isocyanate terminated basic performed polymer.Linking agent adopts 4-methyl-2.6-diaminostilbene, 3 benzene diformazan mercaptos, dosage of crosslinking agent among NH2 in the linking agent (NH2 is 9.0mmol/g, down with) and the component A-mol ratio of NCO is 0.88.Anti-aging agent adopts 2,6 ditertiary butyl p cresol.Aging inhibitor dosage is 0.1% of isocyanate terminated basic performed polymer (component A) weight ratio.Solvent adopts organic pure pimelinketone, and consumption is 250% of a linking agent weight.
Make the high-performance multipurpose urethane elastomerics at last: A component and B components by weight are 2.2:1.Mixing and stirring, room temperature was solidified 90 hours.The high-performance multipurpose urethane elastomer product tensile strength that obtains: 37.11MPa, elongation at break 380%, 300% tensile modulus: 34.00MPa.
Embodiment 4
At first prepare performed polymer (component A): in the there-necked flask of 3 liters, add 3100 gram terminal hydroxy polybutadiene liquid rubber.The molecular-weight average of terminal hydroxy polybutadiene liquid rubber is 3321, average functionality 2.89, and hydroxyl value is at 0.5868mmol/g.Be heated to 100 ± 1 ℃, vacuumize 30min, be cooled to 50 ℃ then, add 4,4 ,-diphenylmethanediisocyanate 631 grams.The intensification polymerization temperature reacted 0.5 hour between 85 ℃, was cooled to 75 ℃, and isothermal reaction 5.0h vacuumizes 30min then, and obtaining the middle NCO% of isocyanate terminated basic butyronitrile fluid rubber performed polymer (component A) is 6.77, cooling discharge.
Refabrication performed polymer (component A): in the there-necked flask of 3 liters, add 1800 gram hydroxy-terminated polybutadienes-vinyl cyanide fluid rubbers.The molecular-weight average of hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber is 2873, average functionality 2.5, and itrile group binding capacity 14.92%, hydroxyl value is at 0.4844mmol/g.Be heated to 100 ℃, vacuumize 30min, be cooled to 50 ℃ then, add 4,4 ,-diphenylmethanediisocyanate 1123 grams.The intensification polymerization temperature reacted 1 hour between 95 ℃, was cooled to 70 ℃, and isothermal reaction 4.5h vacuumizes 30min then, and obtaining the middle NCO% of isocyanate terminated basic butyronitrile fluid rubber performed polymer (component A) is 12.78, cooling discharge.
Preparation solidifying agent (B component): chainextender adopts N, and N is two-derivative of 2-hydroxypropyl-aniline, its consumption with NCO in the mol ratio of OH in the chainextender and the isocyanate terminated basic performed polymer between 0.075.Linking agent adopts 3,3 ,-two chloro-4,4 ,-diamino-ditan, dosage of crosslinking agent with among NH2 in the linking agent and the component A-mol ratio of NCO is between 1.0.Anti-aging agent adopts 2,6 ditertiary butyl p cresol.Aging inhibitor dosage is 0.15% of isocyanate terminated basic performed polymer (component A) weight ratio.Solvent adopts the mixed thing of pimelinketone and 2-butanone, and consumption is 60% of a linking agent weight.
Make the high-performance multipurpose urethane elastomerics at last: 2 kinds of A components and a kind of B components by weight are 2.5:1.Mixing and stirring, room temperature was solidified 90 hours.The high-performance multipurpose urethane elastomer product tensile strength that obtains: 17.11MPa, elongation at break 341%, 300% tensile modulus: 14.00MPa.
Represent to prepare component A respectively in the tabulation mode below; Preparation B component and component A and the mixing cured elastomeric embodiment of high-performance multipurpose urethane that makes of B component.
Preparation component A sees Table 1, and the preparation B component sees Table 2, and A, the B component is mixing cured sees Table 3.
Table 1
Polyether glycol/% Polyisocyanates/% Initial reaction time/min The initial reaction temperature/℃ Late phase reaction time/h The late phase reaction temperature/℃
1 Terminal hydroxy polybutadiene liquid rubber molecular-weight average is 3988, average functionality 2.6, and hydroxyl value is at 0.5019mmol/g.Consumption 1800 grams 4,4 ,-diphenylmethanediisocyanate, consumption 1210 grams 40 90 5.0 75
2 Hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber molecular-weight average is 3197, average functionality 2.7, and itrile group binding capacity 20.74%, hydroxyl value is at 0.4257mmol/g.Consumption 1700 grams Hexamethylene diisocyanate, consumption 420 grams 50 95 4.5 85
3 PTMG molecular-weight average 1350, average functionality 2.9, hydroxyl value is at 1.3993mmol/g, and consumption 1500 restrains 4,4 ,-diphenylmethanediisocyanate, consumption 640 grams 30 85 3.0 70
4 Hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber molecular-weight average is 2875, average functionality 2.4, and itrile group binding capacity 14.92%, hydroxyl value is at 0.4844mmol/g.Consumption 1800 grams Tolylene diisocyanate, consumption 600 grams 40 90 4.0 85
5 Terminal hydroxy polybutadiene liquid rubber molecular-weight average is 3988, average functionality 2.6, and hydroxyl value is at 0.3899mmol/g.Consumption 1800 grams Tolylene diisocyanate, consumption 493 grams 60 95 4.5 80
Table 2
Chainextender consumption OH/NCO (mol ratio) Dosage of crosslinking agent NH 2/ NCO (mol ratio) Anti-aging agent/% (weight percent of component A) Solvent/% (weight percent of linking agent)
1 0.08 (0.8 using MOCA) (0.1 with 2246) 40 (dehydrated alcohols)
2 0.09 (0.9 using MOCA) (0.11 with 2246) 100 (2-butanone is composite)
3 0.10 (1.05 using H30) (0.12 with 2246) 50 (pimelinketone and 2-butanone are composite)
4 0.11 (1.1 using H30) (0.13 with 264) 100 (2-butanone)
5 0.075 (1.2 using H30) (0.14 with 264) 250 (acetone and 2-butanone are composite)
Table 3
The A:B weight percent Set time/h Tensile strength/MPa Elongation at break/% 300% tensile modulus/MPa
1 2.35 80 19.32 321 13.21
2 2.1 90 13.22 351 12.01
3 3.4 100 45.00 421 41.32
4 1.4 100 15.01 322 13.54
5 1.0 90 18.71 319 14.02
Comparative example 1
In the there-necked flask of 3 liters, add 1800 gram hydroxy-terminated polybutadienes-vinyl cyanide fluid rubbers, be heated to 100 ± 5 ℃, vacuumize 30min, be cooled to 50 ℃ then, add tolylene diisocyanate 143 grams, be warming up to 80 ℃, isothermal reaction 1.5h, viscosity increases gradually, and seize becomes gel group.Hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber consumption is described when tolylene diisocyanate consumption<10%〉90% o'clock, can not generate performed polymer.
Comparative example 2
Add 1800 gram hydroxy-terminated polybutadienes-vinyl cyanide fluid rubbers in the there-necked flask of 3 liters, the molecular-weight average of hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber is 2789, average functionality 2.3, and itrile group binding capacity 16.09%, hydroxyl value is at 0.4806mmol/g.Be heated to 100 ± 5 ℃, vacuumize 30min, be cooled to 50 ℃ then, add tolylene diisocyanate 714 grams, be warming up to 80 ℃, isothermal reaction 5.0h, vacuumize 30min then, obtain that NCO% is 2.93 in the isocyanate terminated basic butyronitrile fluid rubber performed polymer, cooling discharge;
B component is with embodiment 1;
Make the high-performance multipurpose urethane elastomerics at last: A component and B components by weight are 0.8:1.Mixing and stirring, room temperature was solidified 120 hours, and is uncured.When the ratio that A and B be described exceeded the 1.0-6.0 scope, complete reaction was intact for active group in the mixture, and product is uncured.
Comparative example 3
Preparation performed polymer (component A): identical with embodiment 3.
Preparation solidifying agent (B component): without chainextender.Linking agent adopts 3,3 ,-two chloro-4,4 ,-diamino-ditan, dosage of crosslinking agent with among NH2 in the linking agent and the component A-mol ratio of NCO is between 1.0.Do not use anti-aging agent.Solvent adopts organic pure pimelinketone, and consumption is 250% of a linking agent weight.
Make the high-performance multipurpose urethane elastomerics at last: A component and B components by weight are 1.8:1.Mixing and stirring, room temperature was solidified 100 hours.The The PU products tensile strength that obtains: 19.01MPa, elongation at break 161%, 300% tensile modulus: 13.70MPa.
The result shows, adopts polyurethane curing agent MOCA commonly used to solidify same performed polymer, the elastomerics that obtains, and performance differs about 1 times.

Claims (6)

1. synthesis method of high-performance multipurpose urethane elastomer, it is characterized in that: with terminal hydroxy group class I liquid I rubber or polytetrahydrofuran ether alcohol, with the polyisocyanates reaction, under the reaction times of stipulating, temperature, make isocyanate terminated basic performed polymer, be the A component; Compound with chainextender, solvent, anti-aging agent and linking agent, obtain solidifying agent, be the B component; A component and B component are mixed in proportion at room temperature solidifies, and makes the high-performance multipurpose urethane elastomerics;
Described A component and B components by weight between 1.0-6.0:1, mixing and stirring, condition of cure is: room temperature, 80-100 hours set times;
Described chainextender is N, and N is two-derivative of 2-hydroxypropyl-aniline, its consumption with NCO in the mol ratio of OH in the chainextender and the isocyanate terminated basic performed polymer between 0.075-0.11;
Described linking agent is 3,3 ,-two chloro-4,4, a kind of in-diamino-ditan or the 4-methyl-2.6-diaminostilbene, 3 benzene diformazan mercaptos, dosage of crosslinking agent with among NH2 in the linking agent and the component A-mol ratio of NCO is between 0.80-1.2;
Described anti-aging agent is 2,6 ditertiary butyl p cresol or 2, a kind of in 2-methylene double-basis-4-methyl-6-tert butyl-phenol, and the weight ratio of anti-aging agent component A is 0.1-0.15%;
Described solvent is organic alcohol or ketone, and wherein organic alcohol is dehydrated alcohol; Ketone comprises: acetone, 2-butanone, pimelinketone; Solvent load is the 40-300% of linking agent weight.
2. synthesis method of high-performance multipurpose urethane elastomer according to claim 1, it is characterized in that: described terminal hydroxy liquid rubber is a kind of in terminal hydroxy polybutadiene liquid rubber or the hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber, wherein: the molecular-weight average of terminal hydroxy polybutadiene liquid rubber is 3000-4000, average functionality 2-4, hydroxyl value is at 0.4-0.9mmol/g; The molecular-weight average of hydroxy-terminated polybutadienes-vinyl cyanide fluid rubber is 2000-3500, average functionality 2-4, and itrile group binding capacity 14-25%, hydroxyl value is at 0.4-0.7mmol/g; The molecular-weight average of described polytetrahydrofuran ether alcohol is between 800-1500, and average functionality is between 2-4, and hydroxyl value is between 1.3-1.9mmol/g.
3. synthesis method of high-performance multipurpose urethane elastomer according to claim 1, it is characterized in that: polyisocyanates comprises tolylene diisocyanate (TDI), 4,4,-diphenylmethanediisocyanate (MDI), 1, a kind of in 5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI) or the PPDI (PPDI).
4. synthesis method of high-performance multipurpose urethane elastomer according to claim 1, it is characterized in that: the prescription of preparation A component: the weight of terminal hydroxy group class I liquid I rubber or PTMG alcoholic solution is between 60-90%, and the weight of polyisocyanates is between 10-40%; Polymerization temperature reacted 0.5-1 hour between 85-95 ℃, was cooled to 70-85 ℃ of isothermal reactions 2.5-5.0 hours, and NCO% is between 2-20% in the synthetic performed polymer that obtains.
5. a kind of synthesis method of high-performance multipurpose urethane elastomer according to claim 1, it is characterized in that: described high-performance multipurpose urethane elastomerics can be according to requirements of different users, select different material for use, do any adjustment, performed polymer mixes with composite curing agent, after at room temperature solidifying, and tensile strength: 10.0-47.0MPa, elongation at break〉300%, 300% tensile modulus: 5-35.0MPa.
6. according to claim 1 or 2 or 3 or 4 or 5 described a kind of synthesis method of high-performance multipurpose urethane elastomer, it is characterized in that: the polyurethane elastomer preparation process adopts two kinds of different A components to mix with a kind of B component.
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CN102604038B (en) * 2012-03-01 2013-11-06 深圳市乐普泰科技股份有限公司 Transparent polyurethane elastomer and preparation method as well as application
CN102643408A (en) * 2012-04-25 2012-08-22 北京化工大学 Preparation method of polyurethane elastomer for engineering tire treads
CN103044654B (en) * 2012-12-13 2015-06-03 华南理工大学 Polyurethane elastomer with long alkyl branch, preparation method thereof and application thereof
JP2017525814A (en) * 2014-08-18 2017-09-07 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Polyester-modified polybutadienol for producing polyurethane elastomers and thermoplastic polyurethanes
RU2735229C2 (en) * 2014-12-19 2020-10-29 Стрейт Эксесс Текнолоджиз Холдингз (Пти) Лтд Polyurethanes
CN105461891B (en) * 2015-12-15 2019-06-18 中昊北方涂料工业研究设计院有限公司 A kind of flexible polyurethane resin and preparation method thereof with good heat resistance
CN105542114B (en) * 2016-01-29 2018-01-02 上海益弹新材料有限公司 TPUE containing cyano group and preparation method thereof in a kind of soft segment
CN105885005A (en) * 2016-06-22 2016-08-24 北京石油化工学院 Preparation method of polyurethane elastomer material
CN108559058A (en) * 2018-05-11 2018-09-21 美瑞新材料股份有限公司 A kind of high transparency thermoplastic polyurethane elastomer and preparation method thereof
CN111057207A (en) * 2018-10-17 2020-04-24 上海浦加钻采技术有限公司 Prepolymer of elastomer material for screw drilling tool and preparation method thereof
CN111055412B (en) * 2018-10-17 2021-08-10 上海浦加钻采技术有限公司 Forming method for producing screw drill stator by using elastomer material
CN109535380B (en) * 2018-12-19 2021-01-26 广州机械科学研究院有限公司 Heat-crosslinking thermoplastic polyurethane elastomer and preparation method and application thereof
CN109679070B (en) * 2018-12-29 2021-10-12 上海优玥新材料科技有限公司 Yellowing-resistant high-transmittance damping material and preparation method thereof
CN110964171B (en) * 2019-12-20 2022-03-11 万华化学集团股份有限公司 Polyurethane polyurea water dispersion and preparation method and application thereof
CN115286988B (en) * 2022-08-16 2024-01-23 中国航发北京航空材料研究院 Elastic protective coating for flexible substrate and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998056841A1 (en) * 1997-06-11 1998-12-17 Stowe Woodward Company Castable polyurethane elastomers for industrial rollers
CN1245817A (en) * 1998-08-26 2000-03-01 美国拜尔公司 Thermoplastic polyurethane (TPU based on polybutadiene soft chain segment) composite and its preparation method
US6211324B1 (en) * 1999-06-08 2001-04-03 Bayer Corporation Hydrophobic polyurethane elastomer
US6780957B1 (en) * 1999-12-29 2004-08-24 Bayer Polymers Llc Hydrophobic light stable polyurethane elastomer with improved mechanical properties

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5994466A (en) * 1996-06-12 1999-11-30 Stowe Woodward Company Castable polyurethane elastomers for industrial rollers
WO1998056841A1 (en) * 1997-06-11 1998-12-17 Stowe Woodward Company Castable polyurethane elastomers for industrial rollers
CN1245817A (en) * 1998-08-26 2000-03-01 美国拜尔公司 Thermoplastic polyurethane (TPU based on polybutadiene soft chain segment) composite and its preparation method
US6211324B1 (en) * 1999-06-08 2001-04-03 Bayer Corporation Hydrophobic polyurethane elastomer
US6780957B1 (en) * 1999-12-29 2004-08-24 Bayer Polymers Llc Hydrophobic light stable polyurethane elastomer with improved mechanical properties

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