CN1073126C - Method for preparing end amino or polyamino polymer - Google Patents

Method for preparing end amino or polyamino polymer Download PDF

Info

Publication number
CN1073126C
CN1073126C CN97106263A CN97106263A CN1073126C CN 1073126 C CN1073126 C CN 1073126C CN 97106263 A CN97106263 A CN 97106263A CN 97106263 A CN97106263 A CN 97106263A CN 1073126 C CN1073126 C CN 1073126C
Authority
CN
China
Prior art keywords
agent
aminolysis
initiator
formula
sulfo group
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
CN97106263A
Other languages
Chinese (zh)
Other versions
CN1180076A (en
Inventor
胡春圃
华峰君
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.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
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 East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN97106263A priority Critical patent/CN1073126C/en
Publication of CN1180076A publication Critical patent/CN1180076A/en
Application granted granted Critical
Publication of CN1073126C publication Critical patent/CN1073126C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

The present invention relates to a novel method for preparing terminal amino polymers or polyamino polymers. Terminal hydroxyl polyolefine or terminal hydroxyl polyoxyalkylene is used as an initiator. Firstly, sulfonic esterification is carried out to sulfuryl chloride, and then an amidolysis agent is used for the amidolysis of obtained terminal sulfonated polyester compounds. The method has mild reaction conditions, and raw materials are easy to obtain. The obtained product with favorable fluidity can be widely used in the fields of washing material, amine adhesives, plastics, petroleum, textile, printing and dyeing, etc.

Description

A kind of new method for preparing end amido or polyamines based polyalcohol
The present invention relates to a kind of macromolecular compound--the synthetic method of end amine based polymer and polyamines based polyalcohol.
End amine based polymer and polyamines based polyalcohol have in fields such as coating, tackiness agent, plastics, oil, weaving and printing and dyeing very to be used widely.At present, the method for preparing end amine based polymer and polyamines based polyalcohol is a lot, United States Patent (USP) (1) USP4202987, (2) 4191835, (3) 379261, (4) 4187367 grades all disclose preparation method separately, and (Guangzhou chemistry) also disclosed a kind of method for preparing polyether polyamine in 1991.Aforesaid method all existed many defectives in implementing kind, the polymericular weight of the described method preparation of document (1) is little, and the fusing point height is difficult for mixing with Resins, epoxy, and the solidification value height of cured epoxy resin; And the disclosed technology of other documents also all exists severe reaction conditions, and environmental pollution is serious, and various defectives such as raw material sources difficulty need a kind of new preparation method of development research to satisfy demand of practical production for this reason.
The objective of the invention is to overcome the shortcoming of prior art, proposing a kind of is the initial action raw material from terminal hydroxy group polyolefine or terminal hydroxy group polyoxygenated alkene directly, at normal temperatures and pressures, by simple reactions steps, prepares the method for end amido or polyamines based polyalcohol.
Design of the present invention is such:
(1) is initiator with terminal hydroxy group polyolefine or terminal hydroxy group polyoxygenated alkene, carries out the sulphur esterification, terminal hydroxy group is sealed, form end sulfo group carboxylate with SULPHURYL CHLORIDE.
(2) above-mentioned carboxylate is used aminolysis agent aminolysis, connected amido, can obtain said end amido or polyamines based polyalcohol at polyolefine or polyoxyalkylene hydrocarbon molecule two ends.
(3) select the molecular weight and the hydroxy functional group number of different terminal hydroxy group polyolefine and terminal hydroxy group polyoxygenated alkene, can obtain to have the amine based polymer of different molecular weight and functional group's number; Select different aminolysis agent,, just can obtain to have the polymkeric substance of corresponding amido at two ends as polyamines, primary monoamine and secondary amine compound.
The present invention also is achieved in that
The structural formula of end amine based polymer of the present invention and polyamines based polyalcohol is respectively shown in formula (1) and the formula (2):
Figure C9710626300041
Figure C9710626300051
Wherein: R 1Be C nH 2n, C nH nAmong the N-one;
In n=2～6 one;
R 2Be H, CH 3, C 6H 5In one;
R 4, R 3Be H, CH 3, among the OH one;
R 5Be H, CH 3In one;
X be H, OH, CH 3In one;
M is 20～200;
L is 5～200.
The initiator that adopts during polymkeric substance shown in the preparation formula (1) is the terminal hydroxy group polyolefine, and its structural formula is shown in the formula (3), and USP3157604 discloses the preparation method of compound shown in the formula (3),
Figure C9710626300053
During polymkeric substance shown in the preparation formula (2), the initiator of employing is the terminal hydroxy group polyoxygenated alkene with different functional groups degree, and its structural formula is shown in the formula (4), J.Chem.Soc., and 1345, (1959) disclose the preparation method of compound shown in the formula (4),
Figure C9710626300054
Wherein: R 2, R 5, m, L be all same as above.The contriver has proposed following synthetic method through studying for a long period of time:
1. formula (3) or the described initiator of formula (4) are placed the reactor that stirring, heating and reflux are housed; adding catalyzer, sulfonyl agent carry out the sulphur esterification; temperature of reaction is-5 ℃～40 ℃; best esterification temperature is-5 ℃～20 ℃; react under normal pressure and nitrogen protection, the reaction times is 6～10 hours, and it is extremely neutral with the saturated common salt water washing that products therefrom filters the back; isolate supernatant liquid, can obtain end sulfo group carboxylate.
The reaction expression that initiator shown in the formula (3) carries out the sulphur esterification is:
Figure C9710626300055
The reaction expression that initiator shown in the formula (4) carries out the sulphur esterification is:
Figure C9710626300061
Wherein: R 2, R 5All same as above.
Described sulphur esterifying agent is Tosyl chloride or Methanesulfonyl chloride; Described sulphur catalyst for esterification is triethylamine or pyridine and composition thereof, and wherein the result of use of triethylamine is even more ideal.The mol ratio of initiator and SULPHURYL CHLORIDE is 1: 5 to 1.2: 1.
2. will hold get final product behind the sulfo group carboxylate aminolysis the compound shown in formula (1) or the formula (2).The reaction expression that is carried out aminolysis by the end sulfo group carboxylate of formula (3) preparation is:
The reaction expression that is carried out aminolysis by the sulfo group carboxylate of formula (4) preparation is:
Figure C9710626300063
Wherein: R 1, R 2, R 3, R 4, R 5All same as above.
The aminolysis process is as follows: have in the reactor of stirring, heating and reflux one, add aminolysis agent and precipitation agent, drip above-mentioned end sulfo group carboxylate and carry out aminolysis under normal pressure, the aminolysis temperature is 80～150 ℃, optimum temps is 80～130 ℃, and the reaction times is 6～8 hours.Reaction product is filtered, and it is end amido shown in formula (1) or the formula (2) or polyamines an aromatic plant metioned in ancient books polymkeric substance that the vacuum removal solvent promptly gets structural formula:
Described aminolysis agent is the compound with following structure:
Figure C9710626300064
Wherein: R 1, R 3, R 4All same as above, Y is H, OH, CH 3, In a kind of, as mphenylenediamine, piperazine, butylamine, Ursol D and Yi Bingchunan etc.; Described precipitation agent is machine solvents such as toluene, hexanaphthene and benzene, and the mol ratio of aminolysis agent and end sulfo group carboxylate is 3: 1 to 1: 1, and precipitation agent and end sulfo group carboxylate volume ratio are 4: 1 to 2: 1.
Adopt method of the present invention, raw material is easy to get, the reaction conditions gentleness, and the molecular weight of products therefrom is 600～6000, good fluidity easily mixes with other high molecular polymer.
Embodiment one
With terminal hydroxy group polyhutadiene (M n=2000, hydroxyl value 55mgKOH/g) 54g, Tosyl chloride 124g, pyridine 30.3g add in the there-necked flask, holding temperature-5 ℃, stirring and dissolving.Reaction times is 16 hours.After-filtration is finished in reaction, gets light yellow liquid, and washing is got upper strata liquid to neutral in the impouring saturated aqueous common salt.Get another there-necked flask (the stirring and refluxing device is arranged), add mphenylenediamine 30.5g, precipitation agent toluene 90ml, be warmed up to 100 ℃, begin to reflux, be added dropwise to above-mentioned esterifying liquid, react after 10 hours, the cooling, filter light yellow liquid, vacuum is sloughed solvent and mphenylenediamine, promptly gets polyamines base polyhutadiene.
Its total reaction productive rate is 91.2%, and number average functional group degree is 5.4, and viscosity is 3.1PaS.
Embodiment two
Terminal hydroxy group polyhutadiene (Mn=6000, hydroxyl value is 21.3mgKOH/g) 235g replaces the terminal hydroxy group polyhutadiene in the example one, Methanesulfonyl chloride 116g, triethylamine 18.6g, 20 ℃ of holding temperatures, reaction times is 6 hours, and esterification finishes after aminolysis (as described in example 1) is carried out in washing again, wherein the aminolysis agent is pinane piperazine 61g, the aminolysis reaction temperature is 130 ℃, and precipitation agent is a hexanaphthene, must hold the amido polyolefin polymer.
Its total reaction productive rate is 81.9%, and number average functional group number is 1.5.
Embodiment three
Terminal hydroxy group poly styrene polymer (Mn=600, hydroxyl value is 233mgKOH/g) 24.6g replaces the terminal hydroxy group polyhutadiene, and all operating process are as described in the example one.Make the polyamines base polystyrene.
The total reaction productive rate is 86.3%, and functional group's number is 1.6, and viscosity is 0.21PaS.
Embodiment four
With terminal hydroxy group polyoxytrimethylene (Mn=300, hydroxyl value is 244mgKOH/g) 100g, Tosyl chloride 120g, tetrahydrofuran (THF) 60ml drops in the reactor, splashes into triethylamine 40g then, keeps temperature of reaction below 40 ℃, react after 4 hours, to neutral, get the sulphur carboxylate with the saturated common salt water washing.In another reactor, drop into Ursol D 30g, benzene 30ml, temperature of reaction is 80 ℃, reacts after 8 hours, vacuum removal solvent and remaining Ursol D filter and promptly get polyamines base polyoxytrimethylene.
Its total reaction productive rate is 94.7%, and number average functional group number is 5.7, and viscosity is 0.16PaS.
Embodiment five
Hydroxy terminated polyethylene oxide (Mn=2000, hydroxyl value is 55mgKOH/g) 220g replaces the terminal hydroxy group polyoxytrimethylene in the example four, and the aminolysis agent is Yi Bingchunan 45g, and other are operated all with example four.Promptly make end amido polyoxyethylene.
The total reaction productive rate is 92%, and number average functional group number is 1.6, and viscosity is 1.6PaS.
Comparison example
According to the disclosed preparation method of U.S. Pat P4191835, its preparation process is as follows: 46.5g urea and 420g hydroxyl end polyoxytrimethylene amine are joined in the reactor that heating, stirring, backflow and airway are housed, 110 ℃ of holding temperatures, dissolving, reacted 6 hours down at 125～130 ℃, emit 2molNH 3Gas promptly gets thick liquid, this reactant is joined in another reactor that heating, stirring and refluxing and airway are housed, and with the dissolving of 650ml toluene, adds KOH 0.5g, and 80 ℃ of holding temperatures add the 68.7g isatoic anhydride, emit CO 2, after 1.5 hours, use NH 3The OH washing, and refining with chloroform extraction, promptly getting and hold amine based polymer, fusing point is 40 ℃.
By above embodiment and Comparative Examples as seen, preparation process of the present invention is simple, and raw material is easy to get, and molecular weight can be between 600～6000, and good fluidity, are a kind of very promising preparation methods.
Obviously, design disclosed according to the present invention and embodiment are about the professional can adopt other terminal hydroxy group polyolefine with different molecular weight and different hydroxyl values or synthetic said end amido of the present invention of terminal hydroxy group polyoxygenated alkene or polyamines based polyalcohol easily.

Claims (4)

1. a method for preparing end amine based polymer or polyamines based polyalcohol is characterized in that comprising the steps: successively
(1) initiator and catalyzer are placed reactor; under normal pressure and nitrogen protection; carry out the sulphur esterification with sulfonyl agent; reaction times is 6～10 hours; products therefrom is extremely neutral with the saturated common salt water washing; isolate supernatant liquid, obtain a class intermediate product--end sulfo group carboxylate, its reaction expression is respectively shown in formula (a) and the formula (b):
Wherein: R 2Be H, CH 3, C 6H 5, in a kind of; R 5Be H, CH 3In a kind of; M is 20～200; L is 5～200,
Said initiator is terminal hydroxy group polyolefine or terminal hydroxy group polyoxygenated alkene; Said catalyzer is pyridine or triethylamine; Said sulphonating agent is a kind of in toluene sulfonyl chloride or the Methanesulfonyl chloride;
(2) will hold the sulfo group carboxylate to be added drop-wise to and carry out aminolysis reaction in the reactor that aminolysis agent and precipitation agent are housed, react 6～8 hours, product is filtered, the vacuum removal solvent promptly gets said end amine based polymer of the present invention or polyamines based polyalcohol,
Said its general structure of aminolysis agent is:
Figure C9710626300022
Wherein: R 1Be C nH 2n, C nH nAmong the N-one; R 3, R 4Be respectively H, CH 3, among the OH one; Y is H, OH, CH 3, In one; In n=2～6 one; The aminolysis agent is in mphenylenediamine, piperazine, butylamine, Ursol D or the Yi Bingchunan:
The sulphur esterification temperature is-5～40 ℃; The aminolysis temperature is 80～130 ℃; The mol ratio of initiator and sulfonyl agent is 5: 1～1: 1.
2. according to the described method of claim 1, the mol ratio that it is characterized in that initiator and catalyzer is 5: 1～1.2: 1.
3. according to the described method of claim 1, it is characterized in that holding the mol ratio of sulfo group carboxylate and aminolysis agent is 1: 3～1: 1.
4. according to the described method of claim 1, it is characterized in that the volume ratio of precipitation agent and end sulfo group carboxylate is 4: 1～2: 1.
CN97106263A 1997-02-03 1997-02-03 Method for preparing end amino or polyamino polymer Expired - Fee Related CN1073126C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN97106263A CN1073126C (en) 1997-02-03 1997-02-03 Method for preparing end amino or polyamino polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN97106263A CN1073126C (en) 1997-02-03 1997-02-03 Method for preparing end amino or polyamino polymer

Publications (2)

Publication Number Publication Date
CN1180076A CN1180076A (en) 1998-04-29
CN1073126C true CN1073126C (en) 2001-10-17

Family

ID=5168521

Family Applications (1)

Application Number Title Priority Date Filing Date
CN97106263A Expired - Fee Related CN1073126C (en) 1997-02-03 1997-02-03 Method for preparing end amino or polyamino polymer

Country Status (1)

Country Link
CN (1) CN1073126C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504065A (en) * 2011-11-11 2012-06-20 中国石油天然气集团公司 Polyamine inhibitor for drilling fluids and method for preparing polyamine inhibitor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101812147B (en) * 2009-02-19 2011-08-03 中国石油天然气股份有限公司 Amino-terminated polypropylene and preparation method thereof
CN115287907A (en) * 2022-08-23 2022-11-04 江苏陆亿纺织科技有限公司 Wear-resistant anti-yellowing fabric and processing technology thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002598A (en) * 1975-03-06 1977-01-11 Texaco Development Corporation Polyether urea epoxy curing agent
US4007239A (en) * 1970-08-17 1977-02-08 Bayer Aktiengesellschaft Aromatic diamines
US4202987A (en) * 1977-12-09 1980-05-13 Ciba-Geigy Corporation Bis-anthranilates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4007239A (en) * 1970-08-17 1977-02-08 Bayer Aktiengesellschaft Aromatic diamines
US4002598A (en) * 1975-03-06 1977-01-11 Texaco Development Corporation Polyether urea epoxy curing agent
US4202987A (en) * 1977-12-09 1980-05-13 Ciba-Geigy Corporation Bis-anthranilates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504065A (en) * 2011-11-11 2012-06-20 中国石油天然气集团公司 Polyamine inhibitor for drilling fluids and method for preparing polyamine inhibitor

Also Published As

Publication number Publication date
CN1180076A (en) 1998-04-29

Similar Documents

Publication Publication Date Title
Six et al. From star‐shaped to dendritic poly (ethylene oxide) s: Toward increasingly branched architectures by anionic polymerization
Eaton et al. The first catalytic iron-mediated [4+ 1] cyclopentenone assembly: stereoselective synthesis of 2, 5-dialkylidenecyclo-3-pentenones
NZ214401A (en) Star/comb-branched polyamides and polyamines
Nagasaki et al. Primary amino-terminal heterobifunctional poly (ethylene oxide). Facile synthesis of poly (ethylene oxide) with a primary amino group at one end and a hydroxyl group at the other end
CN105367806B (en) A kind of new polyrotaxane and preparation method thereof
US20030018130A1 (en) Hyperbranched polymer domain networks and methods of making same
CN109251260A (en) Active polymerization system based on phosphine base catalysis synthesizing super high molecular weight polymer
CN1642643A (en) Method for preparing metal cyanide catalyst complexes using partially miscible complexing agents
CN1073126C (en) Method for preparing end amino or polyamino polymer
D'Haese et al. Synthesis and reactions of polytetrahydrofuran with thiolanium end groups
CN114308120A (en) Phosphorus salt amphiphilic dual-functional organic catalyst and preparation method and application thereof
US3278484A (en) Organosilicon compounds, methods of preparation and use
CN101367938A (en) Novel fluorine-containing polyamide sulfonylamine polymer and preparation method thereof
CN1130195A (en) Cyclic olefine polymer
CN1068346C (en) Core functionalised star block copolymers
EP0473088B1 (en) Non-crosslinked, polybranched polymers
CN101050276A (en) Polyethyleneglycol of end group of amino acid, and preparation method
EP1794209A1 (en) Polyether polymer matrix
CN112029084B (en) Simple and controllable method for synthesizing alpha-mercapto-omega-hydroxyl polyether by taking thiocarboxylic acid as initiator
CN1133687C (en) Polysilazane with line-ring structure and its preparation method
Huguet et al. Polymerization of oxiranylalkylamines and thiiranylalkylamines derived from achiral and racemic secondary amines
Jenkins et al. Graft copolymers, 2. The application of group‐transfer polymerisation to the synthesis of graft copolymers
CN1088722C (en) Polysiloxane having silazane structure on its main chain
CN101045783A (en) Synthetic process and catalyst preparation of fatty polycarbonate
CN1176120C (en) Technology of preparing comb shaped polymer by combining atomic transfer free radical and ring opening disproportionation polymerization

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee