CN103665291B - A kind of amphoteric ion type hydrophilic chain extender and preparation method thereof - Google Patents

A kind of amphoteric ion type hydrophilic chain extender and preparation method thereof Download PDF

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CN103665291B
CN103665291B CN201310632545.XA CN201310632545A CN103665291B CN 103665291 B CN103665291 B CN 103665291B CN 201310632545 A CN201310632545 A CN 201310632545A CN 103665291 B CN103665291 B CN 103665291B
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chain extender
ethanol
ion type
amphoteric ion
hydrophilic chain
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CN103665291A (en
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王学川
任静
强涛涛
任龙芳
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0833—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups together with anionic or anionogenic groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A kind of amphoteric ion type hydrophilic chain extender and preparation method thereof, be dissolved in ethanol by N methyldiethanol amine and PS, heating reflux reaction 7 ~ 9h, obtains crude product; By the unreacted N methyldiethanol amine in crude product and ethanol removing, obtain solid; Then by solid dehydrated alcohol recrystallization at 30 ~ 40 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.The amphoteric ion type hydrophilic chain extender that the present invention obtains has had negatively charged ion and cationic characteristic concurrently simultaneously, makes the urethane synthesized have good surfactivity.The present invention utilizes the ring-opening reaction of the third sultone, by single step reaction, N methyldiethanol amine and PS is reacted in ethanol, obtains amphoteric ion type hydrophilic chain extender.Synthetic method of the present invention is simple, advantages of nontoxic raw materials or hypotoxicity, and cheap, product solid content is high, pollutes few, have a wide range of applications in polyurethane chain extender industry in the process of production and use.

Description

A kind of amphoteric ion type hydrophilic chain extender and preparation method thereof
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of amphoteric ion type hydrophilic chain extender and preparation method thereof.
Background technology
The relative molecular mass of chainextender is smaller, and reaction is relatively more active, and therefore can effectively regulate the speed of reaction and reaction system is promptly cross-linked, hydrophilic chain extender can make aqueous polyurethane have good dispersiveness or automatic emulsifying performance.Amphoteric ion type hydrophilic chain extender combines the characteristic of negatively charged ion and cationic chainextender, but existing amphoteric ion type hydrophilic chain extender preparation cost is high, and toxicity is stronger.
Summary of the invention
The object of the present invention is to provide that a kind of method is simple, cost is low, amphoteric ion type hydrophilic chain extender that toxicity is lower and preparation method thereof.
In order to achieve the above object, the molecular structure of amphoteric ion type hydrophilic chain extender of the present invention is as follows:
A preparation method for amphoteric ion type hydrophilic chain extender, comprises the following steps:
1) be dissolved in ethanol by N methyldiethanol amine and PS, heating reflux reaction 7 ~ 9h, obtains crude product; Wherein, used PS and the mol ratio of N methyldiethanol amine are 1:(1.1 ~ 1.4);
2) by N methyldiethanol amine unreacted in crude product and ethanol removing, solid is obtained; Then by solid dehydrated alcohol recrystallization at 30 ~ 40 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.
In described step 1), the mass concentration of ethanol is 95%, and the PS of every 0.1mol is molten in the ethanol of 20 ~ 30mL.
Described step 2) in by N methyldiethanol amine unreacted in crude product and ethanol removing concrete grammar be: by crude product petroleum ether extraction, to remove unreacted N methyldiethanol amine, then at 80 ~ 85 DEG C, distill out sherwood oil and ethanol.
Compared with prior art, beneficial effect of the present invention is:
The present invention utilizes the ring-opening reaction of the third sultone, by single step reaction, N methyldiethanol amine and PS is reacted in ethanol, obtains amphoteric ion type hydrophilic chain extender.Therefore, synthetic method of the present invention is simple, cheap, and toxicity is lower; Meanwhile, the present invention consists of and proportioning optimizing materials, and the amphoteric ion type hydrophilic chain extender synthesized is applied to the preparation of urethane, and it is high that it compares urethane solid content prepared by traditional carboxylic acid type chainextender.Sulfonic group is introduced chainextender by the present invention, and obtained amphoteric ion type hydrophilic chain extender, this chainextender has negatively charged ion and cationic characteristic concurrently, makes the urethane synthesized have good surfactivity.Meanwhile, after this amphoteric ion type hydrophilic chain extender is used for the synthesis of urethane, in sulfonic group is incorporated into macromolecular chain, and it is fabulous to have sulfonic polyurethane hydrophilic, therefore, it is possible to improve the performance of urethane each side.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention synthesizes amphoteric ion type hydrophilic chain extender;
Fig. 2 is the infrared spectrogram of amphoteric ion type hydrophilic chain extender of the present invention;
Fig. 3 is the nuclear magnetic spectrum of amphoteric ion type hydrophilic chain extender of the present invention.
Embodiment
See Fig. 1, preparation method of the present invention comprises the following steps:
1) N methyldiethanol amine and PS being dissolved in mass concentration is in the ethanol of 95%, and heating reflux reaction 7 ~ 9h, obtains crude product; Wherein, used PS and the mol ratio of N methyldiethanol amine are 1:(1.1 ~ 1.4); And the molten mass concentration to 20 ~ 30mL of PS of every 0.1mol is in the ethanol of 95%;
2) by crude product petroleum ether extraction, to remove unreacted N methyldiethanol amine, then at 80 ~ 85 DEG C, distill out sherwood oil and ethanol, obtain solid; By solid dehydrated alcohol recrystallization at 30 ~ 40 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.
Synthetic method of the present invention is simple, and product solid content is high, with low cost, pollutes little, has a wide range of applications in the field of synthesis aqueous polyurethane.The present invention utilizes ring-opening reaction, makes N methyldiethanol amine and PS back flow reaction in 95% ethanol, and the product obtained obtains amphoteric ion type hydrophilic chain extender through steps such as extraction, distillation, recrystallizations, and its molecular structure is as follows:
Below in conjunction with embodiment, preparation method of the present invention is described in further details.
Embodiment 1:
1) N methyldiethanol amine and PS being dissolved in mass concentration is in the ethanol of 95%, and heating reflux reaction 7h, obtains crude product; Wherein, used PS and the mol ratio of N methyldiethanol amine are 1:1.1; And the PS of every 0.1mol molten be in the ethanol of 95% to 20mL mass concentration;
2) by crude product petroleum ether extraction to remove unreacted N methyldiethanol amine, then at 80 DEG C, distill out sherwood oil and ethanol, obtain solid; By solid dehydrated alcohol recrystallization at 30 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.
Embodiment 2:
1) N methyldiethanol amine and PS being dissolved in mass concentration is in the ethanol of 95%, and heating reflux reaction 7h, obtains crude product; Wherein, used PS and the mol ratio of N methyldiethanol amine are 1:1.2; And the PS of every 0.1mol molten be in the ethanol of 95% to 20mL mass concentration;
2) by crude product petroleum ether extraction, to remove unreacted N methyldiethanol amine, then at 80 DEG C, distill out sherwood oil and ethanol, obtain solid; By solid dehydrated alcohol recrystallization at 30 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.
Embodiment 3:
1) N methyldiethanol amine and PS being dissolved in mass concentration is in the ethanol of 95%, and heating reflux reaction 8h, obtains crude product; Wherein, used PS and the mol ratio of N methyldiethanol amine are 1:1.3, and the PS of every 0.1mol molten be in the ethanol of 95% to 25mL mass concentration;
2) by crude product petroleum ether extraction, to remove unreacted N methyldiethanol amine, then at 85 DEG C, distill out sherwood oil and ethanol, obtain solid; By solid dehydrated alcohol recrystallization at 35 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.
Embodiment 4:
1) N methyldiethanol amine and PS being dissolved in mass concentration is in the ethanol of 95%, and heating reflux reaction 9h, obtains crude product; Wherein, used PS and the mol ratio of N methyldiethanol amine are 1:1.4, and the PS of every 0.1mol molten be in the ethanol of 95% to 30mL mass concentration;
2) by crude product petroleum ether extraction, to remove unreacted N methyldiethanol amine, then at 85 DEG C, distill out sherwood oil and ethanol, obtain solid; By solid dehydrated alcohol recrystallization at 40 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.
Embodiment 5:
1) N methyldiethanol amine and PS being dissolved in mass concentration is in the ethanol of 95%, and heating reflux reaction 9h, obtains crude product; Wherein, used PS and the mol ratio of N methyldiethanol amine are 1:1.4, and the PS of every 0.1mol molten be in the ethanol of 95% to 30mL mass concentration;
2) by crude product petroleum ether extraction, to remove unreacted N methyldiethanol amine, then at 82 DEG C, distill out sherwood oil and ethanol, obtain solid; By solid dehydrated alcohol recrystallization at 40 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.
As shown in Figure 2,3398.04cm -1the absorption peak that neighbouring of occurring is strong and wide is primary hydroxyl stretching vibration absorption peak, 2956.32cm -1, 2897.63cm -1for-CH 2-stretching vibration absorption peak, 2407cm -1place is CH 3stretching vibration absorption peak, 1195cm -1for S (=O) 2asymmetrical stretching vibration absorption peak, 1084cm -1for S (=O) 2the absorption peak of symmetrical stretching vibration, 943.24cm -1for C-N stretching vibration absorption peak.Tentatively can infer it is required product amphoteric ion type hydrophilic chain extender thus.
As shown in Figure 3, on each group, H chemical shift δ is :-C-CH 2-C-SO 3 -, 2.32 ~ 2.48(m, 2H);-N-CH 2-C-C-SO 3 -, 3.00 ~ 3.12(t, 2H);-CH 3, 3.32(s, 3H);-CH 2-SO 3 -, 3.41 ~ 3.50(t, 2H);-N-CH 2-C-O-, 3.52 ~ 3.61(t, 4H);-N-C-CH 2-O-, 3.96 ~ 4.12(m, 4H).4.70 be solvent peak.This collection of illustrative plates meets the chemical structure of target product amphoteric ion type hydrophilic chain extender.
By (1.5 ~ 2): the mol ratio of 1, poly adipate succinic acid ester (PBA) and isophorone diisocyanate (IPDI) is added in four-hole boiling flask, then at 95 DEG C of reaction 2h, be cooled to 70 DEG C again, performed polymer is obtained after continuing reaction for some time at 75 DEG C after adding catalyzer, then adding acetone makes performed polymer cool to 60 DEG C, finally add amphoteric ion type hydrophilic chain extender and carry out chain extension, the consumption of amphoteric ion type hydrophilic chain extender is 7% ~ 9% of PBA and IPDI quality summation, deionized water emulsification is added under rapid stirring, underpressure distillation afterwards goes out acetone, then obtain aqueous polyurethane dispersion.Product prepared by experiment proves can play the effect of chain extension.
The present invention utilizes the ring-opening reaction of the third sultone, by single step reaction, N methyldiethanol amine and PS is reacted in ethanol, obtains amphoteric ion type hydrophilic chain extender.Synthetic method of the present invention is simple, advantages of nontoxic raw materials or hypotoxicity, and cheap, product solid content is high, pollutes few, have a wide range of applications in polyurethane chain extender industry in the process of production and use.

Claims (3)

1. a preparation method for amphoteric ion type hydrophilic chain extender, is characterized in that, comprises the following steps:
1) be dissolved in ethanol by N methyldiethanol amine and PS, heating reflux reaction 7 ~ 9h, obtains crude product; Wherein, used PS and the mol ratio of N methyldiethanol amine are 1:(1.1 ~ 1.4);
2) by N methyldiethanol amine unreacted in crude product and ethanol removing, solid is obtained; Then by solid dehydrated alcohol recrystallization at 30 ~ 40 DEG C, final drying, obtains amphoteric ion type hydrophilic chain extender.
2. the preparation method of amphoteric ion type hydrophilic chain extender according to claim 1, is characterized in that: described step 1) in the mass concentration of ethanol be 95%, and the PS of every 0.1mol is molten in the ethanol of 20 ~ 30mL.
3. the preparation method of amphoteric ion type hydrophilic chain extender according to claim 1, it is characterized in that: described step 2) in by N methyldiethanol amine unreacted in crude product and ethanol removing concrete grammar be: by crude product petroleum ether extraction, to remove unreacted N methyldiethanol amine, then at 80 ~ 85 DEG C, distill out sherwood oil and ethanol.
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CN105037217B (en) * 2015-06-17 2017-04-12 南京博炫生物科技有限公司 Preparation method for biological buffer agent
CN109251291A (en) * 2017-07-12 2019-01-22 广州冠志新材料科技有限公司 A kind of alicyclic sulfonic acid type hydrophilic chain extending agent and preparation method thereof
CN110606815A (en) * 2019-07-31 2019-12-24 浙江大川新材料股份有限公司 Preparation method of sulfonic acid type chain extender
CN110358039B (en) * 2019-08-28 2021-05-04 盐城工学院 Preparation method of self-coloring polyurethane based on zwitterion, product and application thereof
CN112500772B (en) * 2019-09-16 2022-06-28 天津大学 Betaine cation waterborne polyurethane antibacterial coating and preparation method thereof
CN114957597A (en) * 2021-02-25 2022-08-30 贝克顿·迪金森公司 Polyurethane-type medical article
CN113135846A (en) * 2021-04-07 2021-07-20 吉和昌新材料(荆门)有限公司 Preparation method of sulfobetaine type waterborne polyurethane chain extender

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009075389A1 (en) * 2007-12-12 2009-06-18 Kansai Paint Co., Ltd. Water-based paint compositions
CN102604023A (en) * 2012-02-27 2012-07-25 陕西科技大学 Sulfoacid/carboxylic acid type hydrophilic chain extender and preparation method thereof
CN103087584A (en) * 2011-10-27 2013-05-08 精工爱普生株式会社 Ink jet resin ink composition, ink jet recording method, and recorded matter

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009075389A1 (en) * 2007-12-12 2009-06-18 Kansai Paint Co., Ltd. Water-based paint compositions
CN103087584A (en) * 2011-10-27 2013-05-08 精工爱普生株式会社 Ink jet resin ink composition, ink jet recording method, and recorded matter
CN102604023A (en) * 2012-02-27 2012-07-25 陕西科技大学 Sulfoacid/carboxylic acid type hydrophilic chain extender and preparation method thereof

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