CN1600797A

CN1600797A - Hydrophilic macromonomer and preparation method

Info

Publication number: CN1600797A
Application number: CN 03158329
Authority: CN
Inventors: 方治齐
Original assignee: Hefei University of Technology
Current assignee: Hefei University of Technology; Hefei Polytechnic University
Priority date: 2003-09-22
Filing date: 2003-09-22
Publication date: 2005-03-30
Anticipated expiration: 2023-09-22
Also published as: CN1247646C

Abstract

At first, vulcabond and polyethylene glycol are proceeded prepolymerization, adding terminator (methyl) hydrocarbon arrcostab acrylate to stop reacting when prepolymerization reaches a proper degree to obtain hydrophily macromolecule monose with double bonds at a end and hydrocarbon radical at the other end represented by above general formula.

Description

A kind of hydrophilic macromonomer and preparation method thereof

One, technical field

The present invention relates to a kind of fine polymer chemical and preparation method thereof, exactly is a kind of hydrophilic macromonomer by vulcabond, polyoxyethylene glycol and hydroxyalkyl acrylate preparation and preparation method thereof.

Two, background technology

Fine chemistry industry starts from earlier 1970s.Fine chemicals has been contained small molecules chemical and polymer chemistry product.The fine polymer chemical comprises big minute monomer, photosensitive oligopolymer, reactive oligomers, ion exchange resin, polymer catalyst etc.

Macromonomer is meant that the molecular chain one or both ends have a class functionalization macromole of polymerizable group.Polymerizable group can be vinyl, alkynyl, acrylic or heterocyclic radical etc.

Macromonomer can obtain the clear and definite graft copolymer of structure with the small molecule monomer copolymerization, and can integrate antipodal two kinds of performances, as hydrophilic/hydrophobic (being called for short parents, promptly hydrophilic, oleophylic), polar/non-polar, rigid/flexible etc.Therefore the copolymerization of macromonomer and small molecule monomer is the main path of preparation functional high molecule material, particularly prepares parents' graft copolymer with broad prospects for development.(the fine polymer chemical summer space that " fine polymer chemical industry and application " chapter 4 has a chemical functional is just waiting and is writing, chemical industry press, and 2000.09, publish)

Three, summary of the invention

Technical scheme of the present invention is to give polymerization with the same polyoxyethylene glycol of vulcabond (PEG), stops active end group with terminator then and makes reaction terminating, and its product is that an end has two keys, the other end that the hydrophilic macromonomer (being called for short HTP) of hydroxyl is arranged.

Its processing condition are as follows

1, the mol ratio of reactant: polyoxyethylene glycol: vulcabond: terminator=1: 0.7～0.9: 0.2～0.6;

2, temperature of reaction: 70～80 ℃;

3, the reaction times: give poly-reaction 1～3 hour, termination reaction 0.5～1 hour;

4, cool off with solvent or deionized water dilution after reaction finishes.

Described vulcabond can be a TDI (tolylene diisocyanate

) or HDI (hexamethylene diisocyanate OCN-CH ₂CH ₂CH ₂CH ₂CH ₂CH ₂-NCO) or MDI (diphenylmethanediisocyanate Or IPDI or NDI etc.

Described terminator can be (methyl) hydroxyalkyl acrylate, as beta-hydroxy ethyl ester, β-hydroxypropyl acrylate, hydroxypropyl acrylate etc.

Described solvent can be alcohols such as ethanol, propyl alcohol, Virahol, butanols etc., or pure ethers such as glycol ether, propylene glycol etc.

Described hydrophilic macromonomer HTP is with the compound shown in the following general formula:

In the formula:

R ₁: or TDI

Or HDI (CH ₂CH ₂CH ₂CH ₂CH ₂CH ₂-) or MDI

Or the parent of IPDI or NDI etc.

R ₂: or-CH ₂CH ₂-or Or-CH ₂CH ₂CH ₂-etc.

R ₃: or H or-CH ₃

The n:PEG polymerization degree 20～200

The m:HTP polymerization degree 1～10.

The purposes of HTP is very extensive.Itself be a kind of tensio-active agent at first, can be used as emulsifying agent and be used for letex polymerization, for example when vinylformic acid-styrene emulsion polymerization, add HTP, can improve emulsion dielectric medium stability, reduce the latex minimum film-forming temperature, reduce film coalescence aid, reduce latex VOC value etc.Can be used for organic emulsifications such as Resins, epoxy in addition.

HTP and multiple minor comonomer copolymerization must be with the amphiphilic graft copolymers of wetting ability side chain, this multipolymer has multiple use, for example permanently antistatic coating, the saturating wet steam coating of textiles, anti-contamination, easy cleaning coating, surface lubrication coating, surface biological consistency coating, rubber plastic blend compatilizer, plastic working rheological agent, toughner, surface-treated agent etc.

HTP with contain reactive group (OH ,-COOH, NH ₂,

Deng) the minor comonomer copolymerization, by the effect of linking agent crosslinking curing, with various wetting ability side chains securely " dense planting " on the hydrophobic substrates surface, the structure that the waxy leaves that identical fine hair is grown thickly is the same is given this surface permanent hydrophilic performance.Its typical purposes is the air-conditioning heat-exchange fin, and hydrophilic " fine hair " (wetting ability side chain) can be worked to persistence fin under high heat exchange efficiency state, to guarantee the heat pump performance excellence.

Four, embodiment

Non-limiting examples is described below:

1, the there-necked flask that agitator, thermometer and reflux exchanger will be housed places water bath with thermostatic control, at first exsiccant 2molPEG is dropped in the flask, when being warming up to 75 ℃, stirring adds 1.4mol vulcabond TDI reaction 1～3 hour, sampling analysis gives isocyanic acid in the polymers and (adds terminator Propylene glycol monoacrylate 0.4mol when NCO) content is reduced to 0.2～2.0% (weight percent), continue reaction 0.5～1 hour, the dilution of adding solvent butanols, cooling, discharging promptly get product.

2, get PEG 2mol, HDI 1.6mol, hydroxyethyl methylacrylate 0.8mol, 80 ℃ of temperature of reaction, solvent ethylene glycol ether, operation is with embodiment 1.

3, get PEG 2mol, MDI 1.8mol, Hydroxyethyl acrylate 1.2mol, 70 ℃ of temperature of reaction, deionized water, operation is with embodiment 1.

4, in embodiment 1～3, in giving polyreaction, can add organo-tin compound such as stannous octoate or dibutyl tin laurate etc. are made catalyzer, can shorten the reaction times like this, a spot of catalyst residue does not influence use in solution.

Claims

1, a kind of hydrophilic macromonomer is by the compound (HTP) shown in the following general formula:

R ₁: be the parent of vulcabond TDI or HDI or MDI or IPDI or NDI,

R ₂: or-CH ₂CH ₂-or

Or-CH ₂CH ₂CH ₂-,

R ₃: or H or-CH ₃,

N: polyethylene glycol polymeric degree 20～200,

The m:HTP polymerization degree 1～10.

2, a kind of preparation method of hydrophilic macromonomer comprises and gives polyreaction and termination reaction, it is characterized in that: describedly give the polyreaction of giving that polyreaction is polyoxyethylene glycol and vulcabond, described termination reaction is to give the termination reaction of giving polymers and (methyl) hydroxyalkyl acrylate when isocyanic acid content is 0.2～2%wt in the polymers, the mol ratio of reactant is a polyoxyethylene glycol: vulcabond: (methyl) hydroxyalkyl acrylate=1: 0.7～0.9: 0.2～0.6,70～80 ℃ of temperature of reaction, give poly-reaction 1～3 hour, termination reaction 0.5～1 hour.

3, preparation method according to claim 2 is characterized in that: can add the catalyzer organo-tin compound when giving poly-the reaction.

4, preparation method according to claim 3 is characterized in that: described organo-tin compound can be stannous octoate or dibutyl tin laurate.