CN104387550B - A kind of polyurethane and preparation method thereof containing alkynyl - Google Patents

A kind of polyurethane and preparation method thereof containing alkynyl Download PDF

Info

Publication number
CN104387550B
CN104387550B CN201410444215.2A CN201410444215A CN104387550B CN 104387550 B CN104387550 B CN 104387550B CN 201410444215 A CN201410444215 A CN 201410444215A CN 104387550 B CN104387550 B CN 104387550B
Authority
CN
China
Prior art keywords
polyurethane
reaction
containing alkynyl
ptmg
liquid
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.)
Expired - Fee Related
Application number
CN201410444215.2A
Other languages
Chinese (zh)
Other versions
CN104387550A (en
Inventor
何吉宇
唐启恒
杨荣杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Institute of Technology BIT
Original Assignee
Beijing Institute of Technology BIT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing Institute of Technology BIT filed Critical Beijing Institute of Technology BIT
Priority to CN201410444215.2A priority Critical patent/CN104387550B/en
Publication of CN104387550A publication Critical patent/CN104387550A/en
Application granted granted Critical
Publication of CN104387550B publication Critical patent/CN104387550B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/679—Acetylenic compounds
    • 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy 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
    • C08G18/28—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
    • 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
    • C08G18/65—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
    • 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
    • C08G18/70—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
    • 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
    • C08G18/70—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

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 relates to a kind of polyurethane and preparation method thereof containing alkynyl, belongs to heat-resisting material, fire proofing technical field.Liquid polyetherdiol is mixed with liquid diisocyanate, heating carries out addition reaction, and Isosorbide-5-Nitrae butynediols is added, and heating carries out polycondensation reaction and obtains polyurethane of the high temperature resistant containing alkynyl after reaction.The features such as there is the present invention reaction condition mildly to stablize, reproducible, and yield is high, and the period is short is suitble to the production of expansion property；Obtained polymer has excellent high temperature resistant, mechanical strength and the multiple performances such as fire-retardant.

Description

A kind of polyurethane and preparation method thereof containing alkynyl
Technical field
The present invention relates to a kind of high temperature resistant polyurethane and preparation method thereof containing alkynyl, belongs to heat-resisting material, fire-retardant material Expect technical field.
Background technology
Thermoplastic polyurethane elastomer (TPU) is a kind of elastic material between ordinary rubber and plastics, main chain The upper carbamate segment containing repetition, macromolecular main chain are the soft segment and vitrifying by glass transition temperature less than room temperature For temperature higher than made of the rigid chain segment block of room temperature, it has excellent mechanical performance, such as high intensity, high resiliency, Gao Shen Long rate, therefore a series of products such as can be made into rubber, coating, adhesive, waterproof material, are therefore widely used in automobile, machine The fields such as tool, medical treatment and space flight.But it easily burns in air as a kind of high-molecular organic material, flame when burning Very acutely and with black smoke, while there is serious molten drop phenomenon, limit oxygen index (LOI) is only to have between 18-20 Serious fire hazard.Therefore it is a very urgent problem to the heat-resisting and its flame-retardant modified of TPU.
Currently, modification heat-resisting to TPU and fire-retardant mainly passes through physical blending and synthesis inherent flame retardant polymer material Mode.Additive flame retardant is exactly scattered in polymeric substrate by physical blending mode, assigns base material flame retardant property, feature It is that fire retardant is not chemically reacted with the other components in base material and base material, processing technology is simple, using universal, but needs to change Interface compatibility between the kind components such as fire retardant and base material, improves the mechanical property of flame-proofed polymer material, fire retardant is avoided to move Go out.In order to efficiently solve these problems, research more and more concentrates on the side of synthesis inherent flame retardant, heat-resistant polymer material Formula.Fire-retardant, heat-resisting group is introduced into polymer molecular structure by chemically reacting, it is high, heat-resisting to make it have decomposition temperature Property is good, does not allow incendive property.
In recent years, organic polymer of the molecular backbone containing alkynyl is concerned with its special thermal stability.Due to it The network knot that C ≡ C in molecule can be reacted by heat cross-linking or photo-crosslinking keeps intermolecular highly cross-linked formation more stable Structure, thus this kind of polymer usually has higher thermal stability, can be used as high temperature heat-resistant solidification or light-cured resin, becomes resistance to The hot spot of high-temperature material area research.By MOLECULE DESIGN, the glycol of alkynyl will be contained as chain extender, with polytetrahydrofuran ether Glycol (PTMG) and 4,4- methyl diphenylene diisocyanates (MDI) reaction, prepares the novel polyurethane containing alkynyl (TPU)。
Invention content
The purpose of the present invention is preparing a kind of polyurethane containing alkynyl, and propose preparation method.The polyurethane is a kind of The novel high temperature resistant polyurethane material containing alkynyl, contains alkynyl, polyethers, isocyanates, in polymer composites simultaneously Have the function of fire-retardant, high temperature resistant, high strength.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of anti-dropping fire resistant polyimide type polyurethane of the present invention, structural formula are：
Wherein Ar isOrOrIn Any one；N is the degree of polymerization of B,
B is-CH2CH2CH2CH2O-, n=10-45；
Or B is-CH2CH2O-, n=20-500；
Or B isN=10-70；
D isOr
Or Or
In any one；
X is the degree of polymerization, and x=1-10, y are the degree of polymerization, and y=2-15, z are the degree of polymerization, and z=2-15, a are the degree of polymerization, a= 20-90, b are the degree of polymerization, b=35-150.
A kind of preparation method of polyurethane containing alkynyl of the present invention, step are：
1) liquid anhydrous polyetherdiol is mixed with liquid diisocyanate, is stirred, heating carries out addition reaction, heating temperature Degree is 50-100 DEG C, and heating time is 1-15h；Liquid anhydrous polyetherdiol and the molar ratio of liquid diisocyanate are 0.1-1: 1
2) product that step 1) obtains, stirring is added in Isosorbide-5-Nitrae-butynediols, heating carries out polycondensation reaction, and heating temperature is 60-150 DEG C, heating time is 2-24h；The molar ratio of 1,4- butynediols and liquid anhydrous polyetherdiol in step 1) is 0.1- 1:1；
3) product that step 2) obtains after reaction is polyurethane containing alkynyl.
Liquid anhydrous polyetherdiol is polytetrahydrofuran ether glycol, polyethylene glycol or polyethylene oxide-tetrahydrochysene in step 1) One kind in furans ether glycol.The number-average molecular weight of polytetrahydrofuran ether glycol be 1000 ± 50,1400 ± 50,1800 ± 50, 2000 ± 50 or 3000 ± 100.The number-average molecular weight of polyethylene glycol be 1000 ± 50,1400 ± 50,2000 ± 200,4000 ± 400 and 6000 ± 500；8000 ± 500,10000 ± 1500 or 20000 ± 1500.Polyethylene oxide-tetrahydrofuran ether glycol Number-average molecular weight is 1800-6200.
Liquid diisocyanate is in step 1)：4,4 '-methyl diphenylene diisocyanates, Toluene-2,4-diisocyanate, 4- diisocyanates Ester or Toluene-2,4-diisocyanate, one kind in 6- diisocyanate.
The preparation method of liquid 4 in step 1), 4 '-methyl diphenylene diisocyanates is：By 4,4 '-diphenylmethyl of solid Alkane diisocyanate is added in reaction vessel, and heating makes its thawing；Heating temperature is 30-100 DEG C.
The preparation method of liquid anhydrous polyetherdiol is in step 1)：By polyetherdiol in the vacuum drying oven of high temperature, very Moisture is removed under empty condition；The temperature of vacuum drying oven is 100-120 DEG C, removes water time 0.5-20h；Vacuum degree be less than- 0.02MPa。
Advantageous effect
The features such as reaction condition of the present invention is mildly stablized, reproducible, and yield is high, the period is short is suitble to the production of expansion property； It learns that alkynyl modification improves the value of limit oxygen index by test, and also improves polyurethane in UL-94 vertical combustions Grade.In addition, alkynyl is modified the total Heat liberation unit and heat release rate peak value for also reducing polyurethane.
Description of the drawings
Infrared spectrum uses 6700 IR type determination of infrared spectroscopy of NICOLET；Thermal weight loss (TG) uses NETZSCH 209 F1 thermogravimetric analyzers measure, nitrogen atmosphere, 10 DEG C/min of heating rate；Limit oxygen index (rheology science Co., Ltd) according to GB/T 2406.2-2009 tests；UL-94 testing vertical flammabilities are carried out according to UL94-09, and standard sample size 125 × 12.5 × 3.2mm3；Test result is as shown in table 1.
Fig. 1 is the FT-IR spectrograms of the polyurethane of alkynyl prepared by embodiment 1；
Fig. 2 is the thermogravimetric curve figure of the polyurethane containing alkynyl prepared by embodiment 1, and ordinate is mass loss percentage Than；
Fig. 3 is the heat release rate curve figure of the polyurethane containing alkynyl prepared by embodiment 1, and ordinate indicates heat release Rate, unit KW/m2；
Fig. 4 is total hot releasing curve diagram of the polyurethane containing alkynyl prepared by embodiment 1, and ordinate indicates total heat Burst size, unit MJ/m2。
UL-94 vertical combustions, limit oxygen index and the mechanical strength of polyurethane of the table 1 containing alkynyl
Specific implementation mode
Below by embodiment, the invention will be further described, but embodiment is not intended to limit protection scope of the present invention.
Embodiment 1
Prepare MDI：PTMG：The molar ratio of 1,4- butynediols is 2:1:1 polyurethane containing alkynyl, referred to as PU211, PTMG number average molecular weights are 2000；
Raw material is：MDI is 50.0g, and PTMG 200.0g, Isosorbide-5-Nitrae-butynediols is 8.6g,
1) by 200.0g PTMG in the vacuum drying oven of 120 DEG C of high temperature, moisture 2h is removed under vacuum condition；
2) 50.0g solids MDI is added in reaction vessel, makes its thawing under the conditions of 50 DEG C；
3) it will be added in the 50.0g liquid MDIs that step 2) obtains in 200.0g liquid PTMG that step 1) obtains, vacuum item It is stirred under part, addition reaction is carried out under the conditions of 80 DEG C, 1h releases vacuum；
4) 8.6g Isosorbide-5-Nitraes-butynediols is added in the product that step 3) obtains, is stirred, chain extension is carried out under the conditions of 70 DEG C Reaction for 24 hours, obtains the polyurethane TPU211 containing alkynyl.
The reaction route of above-mentioned steps 3 and 4 is as follows：
Table 1

Claims (1)

1. a kind of preparation method of polyurethane containing alkynyl, it is characterised in that：
The raw material that this method uses for：50.0g MDI, 200.0g PTMG and 8.6g Isosorbide-5-Nitraes-butynediols, PTMG data molecules Amount is 2000；
Steps of the method are：
1) by 200.0g PTMG in the vacuum drying oven of 120 DEG C of high temperature, moisture 2h is removed under vacuum condition；
2) 50.0g solids MDI is added in reaction vessel, makes its thawing under the conditions of 50 DEG C；
3) it will be added in the 50.0g liquid MDIs that step 2) obtains in 200.0g liquid PTMG that step 1) obtains, under vacuum condition Stirring, carries out addition reaction under the conditions of 80 DEG C, and 1h releases vacuum；
4) 8.6g Isosorbide-5-Nitraes-butynediols is added in the product that step 3) obtains, is stirred, chain extending reaction is carried out under the conditions of 70 DEG C For 24 hours, the polyurethane TPU211 containing alkynyl is obtained；
Above-mentioned steps 3) and reaction route 4) it is as follows：
The performance of obtained product is as shown in table 1：
Table 1
CN201410444215.2A 2014-09-02 2014-09-02 A kind of polyurethane and preparation method thereof containing alkynyl Expired - Fee Related CN104387550B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410444215.2A CN104387550B (en) 2014-09-02 2014-09-02 A kind of polyurethane and preparation method thereof containing alkynyl

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410444215.2A CN104387550B (en) 2014-09-02 2014-09-02 A kind of polyurethane and preparation method thereof containing alkynyl

Publications (2)

Publication Number Publication Date
CN104387550A CN104387550A (en) 2015-03-04
CN104387550B true CN104387550B (en) 2018-07-20

Family

ID=52605520

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410444215.2A Expired - Fee Related CN104387550B (en) 2014-09-02 2014-09-02 A kind of polyurethane and preparation method thereof containing alkynyl

Country Status (1)

Country Link
CN (1) CN104387550B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110669203B (en) * 2019-09-30 2021-06-04 湖南大学 Intramolecular polyacetylene polyurethane and polytriazole curing system
CN110776616B (en) * 2019-10-26 2021-06-22 福建华夏蓝新材料科技有限公司 Efficient wetting water-based isocyanate curing agent
CN114989393B (en) * 2022-06-28 2024-03-26 岳阳凯门水性助剂有限公司 Polyurethane association thickener and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
聚氨酯弹性体的动态性能研究;宁晓龙;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20111231;B016-173，第24-25页和表3.2 *

Also Published As

Publication number Publication date
CN104387550A (en) 2015-03-04

Similar Documents

Publication Publication Date Title
CN103509167B (en) A kind of anti-dropping fire resistant polyimide type polyurethane and preparation method thereof
CN103242504B (en) Flame-retardant heat-resistance polyurethane resin and preparation method of aqueous emulsion of polyurethane resin
CN109400957B (en) Alkaloid phosphate flame retardant and preparation method thereof
CN104387550B (en) A kind of polyurethane and preparation method thereof containing alkynyl
CN104211900B (en) Polyurethane containing DOPO groups and preparation method thereof
CN103450440B (en) Waterborne polyurethane resin and preparation method thereof
CN104193953B (en) Polyimide-type polyurethane containing DOPO group and preparation method of polyimide-type polyurethane
CN110563765B (en) Synthesis method of Schiff base phosphazene double-base structure flame retardant and modified polyurethane flame retardant
CN107686547B (en) Flame retardant polyurethane and preparation method thereof
CN109251293B (en) Triazine polyurethane charring agent containing furan ring side group and synthesis method thereof
CN105603564B (en) A kind of nitrogen phosphorus synergistic copolymerization flame-proof polylactic acid fiber and preparation method thereof
CN107573479A (en) Utilize the preparation method of the intrinsic modified aqueous polyurethane of phosphorus flame retardant
CN107163825B (en) Environment-friendly flame retardant type water-repellent paint and preparation method thereof
CN115368716A (en) Preparation method of efficient flame-retardant plastic
CN105440565B (en) A kind of hud typed halogen-free flameproof polyformaldehyde composite material and preparation method thereof
CN115850641B (en) Flame-retardant modified polyurethane material and synthesis method thereof
Wang et al. Synthesis and thermal degradation behaviors of hyperbranched polyphosphate
CN106380595A (en) Preparation method of hyperbranched flame retardant and application of hyperbranched flame retardant in polyurethane
CN102199313A (en) Method for preparing low-water-soluble heat-resisting expansion flame retardant
CN113789147B (en) Double-component neoprene composite rubber adhesive and preparation method thereof
CN106478926A (en) A kind of compositionss and preparation method thereof and the application in fire proofing field
CN103319715A (en) Hydrolysis-resistant easy-processable polythioetherimide resin material and preparation method thereof
CN102477139B (en) Halogen-free phosphorus-free resin preparation and halogen-free phosphorus-free low-dielectric flame-retardant composite material
CN104193945A (en) Damp-heat-resistant waterborne polyurethane resin and preparation method thereof
CN112694587B (en) Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180720

Termination date: 20180902

CF01 Termination of patent right due to non-payment of annual fee