CN107903376A - Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application - Google Patents
Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application Download PDFInfo
- Publication number
- CN107903376A CN107903376A CN201711045576.XA CN201711045576A CN107903376A CN 107903376 A CN107903376 A CN 107903376A CN 201711045576 A CN201711045576 A CN 201711045576A CN 107903376 A CN107903376 A CN 107903376A
- Authority
- CN
- China
- Prior art keywords
- glycol
- aqueous polyurethane
- polyurethane dispersion
- solvent
- alcohol
- 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.)
- Pending
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
- C08G18/40—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
- C08G18/08—Processes
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
Abstract
The invention discloses solvent-free aqueous polyurethane dispersion of a kind of continous way and its preparation method and application, preparation method includes the following steps:(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, two terminal hydroxy group Y-shaped pendant hydrophilic chain extender of low melting point and catalyst, preheat respectively, after being then input to mixer disperses mixing, it is input in double-screw reactor and reacts, obtains polyurethane melt;(2) it is injected into shear pump, while water or water with neutralizer is injected into shear pump, shearing is scattered, obtains aqueous polyurethane dispersion;(3) by the aqueous polyurethane dispersion of gained, decrease temperature and pressure, the obtained solvent-free aqueous polyurethane dispersion.The present invention is environmentally protective, and technique is simple, efficient, only needs 30 60min from output is dosed into, improves the stability of production efficiency and product batches;Solvent-free use and continuous automatic production, reduce further production cost, improve the competitiveness of product.
Description
Technical field
The present invention relates to the production method of aqueous polyurethane dispersion.
Background technology
Aqueous polyurethane dispersion is using water as decentralized medium, and only water is volatized into air in use, to ring
Border has no adverse effects.It is nontoxic make it that aqueous polyurethane dispersion also has as decentralized medium using water at the same time, it is tasteless, it is non-ignitable,
The characteristics of not quick-fried safe.Aqueous polyurethane dispersion is as a kind of Environmentally-friepolymer polymer material using extremely wide, replacement oil
Property polyurethane resin is also trend of the times, at present widespread adoption in every field such as synthetic leather, adhesive, building coatings.
Aqueous polyurethane from the end of the sixties in last century industrialize since develop it is extremely rapid, but its production technology or between
Method of having a rest and semi-continuous process, all refer to pre-polymerization in reaction kettle.The problem of maximum during pre-polymerization is that reaction kettle is generally difficult to handle height
Viscous systems, therefore pre- collecting process usually requires addition organic solvent reduction polymerization system viscosity or the molecular weight by prepolymer
It is controlled in extremely low level.After prepolymerization reaction, material is transferred to Scattered Kettle and is neutralized and is disperseed, then is carried out in precipitation kettle
Except solvent.Aqueous polyurethane dispersion prepared by this kind of technique often occurs or molecular weight is low, poor performance, batch are unstable
It is fixed, or the substantial amounts of solvent participation of production process needs, and cannot still participate in polymerizeing after the simple recovery purifying of these solvents
Journey, causes manufacture cost to greatly increase, while while emulsifying is very high to equipment requirement, inefficiency is mass produced, generally from throwing
When expecting that discharging needs 12-16 small.
A kind of new aqueous polyurethane preparation process have developed to this many industry pioneer, i.e., from aggressiveness method work
Skill, also known as " pellet method " technique.Its core thinking prepares polyurethane from interpolymer particles with double-screw reactor, then should be from poly-
Body removes solvent after dissolving in a solvent, obtains large arch dam aqueous polyurethane dispersion.Since the process uses solvent-free participation
Bulk technique and reactionless participation emulsifying process, therefore the molecular weight of dispersion can be greatly improved to be lifted and stablized
Performance, but realize solvent be not required to purifying it is i.e. recyclable, greatly reduce the production cost of water-borne dispersions.Both at home and abroad
There is substantial amounts of worker once or still carry out substantial amounts of research work in this respect now.
Patent CN 102336881A are disclosed with polyester polyol, diisocyanate, small molecule chain extender and hydrophilic list
Body, has also prepared aqueous polyurethane using double screw extruder or casting machine and has been used for Aqueous Polyurethane Adhesives from aggressiveness, and
Achieve good effect;Patent CN 102633971A carried out simple pre-polymerization in advance before raw material enters double-screw reactor
Or DMPA is dissolved with pyrrolidones (NMP), to realize the accurate measurement of DMPA, high temperature and pressure emulsifying technology was produced with reducing
The usage amount of solvent in journey, substantially increases the production efficiency of aqueous polyurethane and reduces environmental pollution, but and unresolved few
Measure operation difficult problem caused by the prepolymer viscosity transient rise under solvent.
Patent CN103382253B substitutes DMPA with glycerine list maleic anhydride ester and glycerine monobutane diacid ester, to realize parent
Dissolving of the water chain extender in small molecule dihydric alcohol, to realize its accurate measurement, so as to smoothly stably prepare aqueous poly- ammonia
After ester disperses from aggressiveness, then in acetone in dissolving, triethylamine neutralization, water, aqueous polyurethane of the acetone up to 30-60% is removed
Dispersion, and the technique is particularly suitable for preparing MDI base high-performance aqueous polyurethane dispersion, can be widely applied to water-based poly- ammonia
The fields such as Lipase absobed leather, adhesive.
The above work employs twin screw techniques to prepare polyurethane melt, successively dissolving, into salt, scattered, de-
The technique such as molten prepares aqueous polyurethane dispersion, and solvent is not purified to reuse.
These above-mentioned techniques solve the simple recycling of the defects of aqueous polyurethane dispersion molecular weight is less than normal and solvent, but
Be without reference to how by urea groups structural response into polyurethane, and can not still be broken away to solvent in scattered, emulsion process
Dependence, can not really prepare not only environmental protection but also have an aqueous polyurethane dispersion of high-performance, high added value.
The content of the invention
The object of the present invention is to provide solvent-free aqueous polyurethane dispersion of a kind of continous way and its preparation method and application,
To overcome defect existing in the prior art.
The method of the present invention, includes the following steps:
(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, two terminal hydroxy group Y-shaped pendant hydrophilic of low melting point
Chain extender and catalyst, are preheated to 60-100 DEG C respectively, after being then input to mixer disperses mixing, are input to twin-screw reaction
Reacted in device, acquisition number-average molecular weight is 30000-200000 polyurethane melts;
The structurally and operationally parameter of the double-screw reactor, it is desirable to which material can axially and radially having very in screw rod
Big shearing divergent function, is overcome measurement deviation on the different time caused by measuring equipment pulse, and inventor has found,
Using 16≤L/D≤56, the double screw extruder of more than rotating speed 200-300rpm, can get a desired effect;
Wherein:L represents spiro rod length, and D represents screw diameter;
In the double-screw reactor, reaction temperature is divided into 7 sections, and first segment is 80-130 DEG C, second segment 100-130
DEG C, the 3rd section is 130-140 DEG C, and the 4th section is 140-150 DEG C, and the 5th section is 150-170 DEG C, and the 6th section is 150-200 DEG C, the
Seven sections are 205-230 DEG C, and residence time of the material in twin-screw is 0.5-3min;
The polymer diatomic alcohol is polyether Glycols, polyester diol, one kind or more in polycarbonate glycol
Kind mixture;
The polyether Glycols use 2 terminal hydroxy groups, and number-average molecular weight is the polyether oligomer of 200-10000, including not
It is limited to:PolyTHF dihydric alcohol (PTMEG), Polyoxypropylene diol (PPG), polyoxyethylene glycol (PEG) and poly-
One or more mixtures of oxypropyleneoxyethylene copolymerization dihydric alcohol (PEPG), mixed proportion are unlimited;
The polyester diol is to contain 2 oligomers of the terminal hydroxy group containing polyester construction, range of number-average molecular weight 200-
4000, including be not limited to:The butyl glycol ester diol of polyadipate -1,4 (PBA), polyethylene glycol adipate glycol (PEA), gather oneself
Two acid propylene glycol ester glycol (PPA), the hexylene glycol of polyadipate -1,6 esterdiol (PHA), polyneopentyl glycol adipate glycol
(PNA), polyadipate ethylene glycol butyl glycol ester diol (PEBA), polyadipate ethylene glycol propylene glycol ester glycol (PEPA), gather oneself
Diacid hexylene glycol neopentyl glycol esterdiol (PHNA), polybutyleneadipate hexylene glycol esterdiol (PBHA), polyadipate fourth two
Alcohol neopentyl glycol esterdiol (PBNA), the one or more mixing for gathering own Inner esterdiols, mixed proportion are unlimited;
The polycarbonate glycol uses the oligomer containing 2 terminal hydroxy group carbonate-containing structures, number-average molecular weight
Scope is 200-4000, is exchanged and synthesized with binary alcohol esters by carbonic diester, including is not limited to:Poly- carbonic acid hexylene glycol esterdiol, gathers
One or more mixtures of neopentyl glycol carbonate esterdiol, polytetramethylene carbonate diol glycol, poly (propylene carbonate) glycol etc.;
The diisocyanate be selected from 4,4- '-diphenylmethane diisocyanates (MDI), toluene di-isocyanate(TDI) (TDI),
Tolylene diisocyanate (XDI), 1,5- how diisocyanate (NDI), paraphenylene diisocyanate (PPDI), hexa-methylene two
One in isocyanates (HDI), isophorone diisocyanate (IPDI), hydrogenation 4,4- '-diphenylmethane diisocyanates (HMDI)
The mixture of kind or any combination;
The small molecule dihydric alcohol is selected from ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,4- butanediols, 1,3- fourths
Glycol, 1,5- pentanediols, neopentyl glycol, 1,6-HD, 1,8- ethohexadiols, hydroquinone hydroxyethyl ether (HQEE), cyclohexyl diformazan
Alcohol, 2- methyl isophthalic acids, one or more kinds of mixtures in ammediol, mixed proportion are unlimited;
The two terminal hydroxy group Y-shaped pendant hydrophilic chain extender of low melting point, preferably dihydromethyl propionic acid and dihydroxymethyl fourth
One kind or mixture in acid, mixed proportion are unlimited;
The catalyst is stannous octoate, dibutyl tin laurate, organic zinc, one kind in organo-bismuth or it is a kind of with
On;
(2) by the polyurethane melt of acquisition, it is continuously injected into shear pump, while water or water with neutralizer is injected
Shear pump, and disperse in 120-200 DEG C of high temperature and 0.2-1.5Mpa down cuts, obtain aqueous polyurethane dispersion;
The neutralizer for triethylamine, dimethylethanolamine, N methyldiethanol amine, triethanolamine, sodium hydroxide and
One or more mixtures in potassium hydroxide;
(3) by the aqueous polyurethane dispersion of gained, 30-50 DEG C is cooled to, and is depressured, is sent into the storage tank with stirring
In, stirring 5~15min of reaction, the obtained solvent-free aqueous polyurethane dispersion, weight solid content is 30-50%;
The solvent-free aqueous polyurethane dispersion, includes the component of following mass percent:
Preferably, the solvent-free aqueous polyurethane dispersion, includes the component of following mass percent:
The above-mentioned aqueous polyurethane dispersion viscosity prepared based on combined type double screw reactor is in 100-2000mpas
(20 DEG C), preferably 200-1000mpas (20 DEG C).
The molecular weight of the aqueous polyurethane dispersion is between 30,000-200,000, to meet institute in practical application
The high anti-tensile requirement of high molecular weight, big cohesive energy, low modulus needed;
Aqueous polyurethane dispersion obtained by this method, can be widely applied to synthetic leather, adhesive, coating, fabric and applies
The every field such as layer, finishing agent, as synthetic leather resin, can be applied to base fabric bottom material resin, surface layer resin, tie layer resins,
The fields such as intermediate layer resin, foaming layer resin.
The present invention is a kind of continous way that aqueous polyurethane dispersion is prepared based on double-screw reactor and shear at high temperature pump
Each raw material of solvent-free production process, i.e. aqueous polyurethane dispersion is realized in double-screw reactor in the short time aggregates into high score
The polymer melt of son amount, during which carries out in the shear pump of high temperature and pressure and and dispersion and emulsion, then after cooling decompression
Into aqueous polyurethane dispersion.The technology utilization twin-screw technique realizes the high molecular weight of aqueous polyurethane, high cohesion energy and height
Performance, and the hydrogen bond of polyurethane is dissociated using high temperature make to slide between strand to substitute traditional solvolysis hydrogen bond
Move, recycle high speed shear pump can be in very short time internal emulsification, so that urea groups is contour instead of high speed dispersor emulsifying process
The advantages that cohesive energy group can be implanted into aqueous polyurethane molecular structure by rear chain extension technique, realize high cohesion energy and heat resistance.
The technique realizes serialization, high performance and the solvent free of aqueous polyurethane dispersion preparation in a word, greatly promotes water-based
The performance and production efficiency of polyurethane, realize the perfect unity of aqueous polyurethane high-performance and low cost.
Compared with existing twin-screw prepares aqueous polyurethane dispersion technique and the water-based technique of traditional acetone prepolymer method, this
Technique can realize following technique effect:
What twin-screw and high speed shear pump can solve high viscosity aqueous polyurethane melt the technique hardly possible such as synthesizes, disperses, emulsify
Topic, process are participated in without solvent, really realize the pure green environmental requirement of aqueous polyurethane;Technique is simple, efficiently, from being dosed into
Output only needs 30-60min, and can realize full continuous automatic production requirement, improves the steady of production efficiency and product batches
It is qualitative;Solvent-free use and continuous automatic production, reduce further production cost, improve the competitiveness of product.
Embodiment
By specific examples below, the present invention is described in detail, but the scope that the present invention is protected is not limited to this
A little embodiments, further include formula adjustment and the process modifications of the non-intrinsically safe done according to the content of the invention.
Pass through the basic performance of dispersions of polyurethanes in the following test method characterization present invention:
The measure of solid content:Weighed up with electronic balance and show that the quality of clean surface plate is M1;2-3g lotions are taken to be placed in
Its quality is referred to as M in surface plate2;Surface plate quality is weighed after when placement 1 is small in 120 DEG C of convection ovens, continues to be put into baking oven,
Until alleged constant mass writes down M3。
Solid content:C=(M3-M1)/(M2-M1) × 100%
Tensile strength:Refer to the stress that material produces maximum uniform plastic deformation.In tension test, sample is until be fractured into
Only suffered maximum tensile stress is tensile strength, can be calculated by maximum load divided by specimen cross section product.
The measure of tensile strength:Dispersions of polyurethanes in the present invention is uniformly coated in polytetrafluoroethylene (PTFE) pallet,
After room temperature dries film forming, the dry 1hr in 120 DEG C of convection ovens, then after 50 DEG C of baking ovens place 8hr, then in test environment
After placing 24hr, its tensile strength is tested with the rate of extension of 100mm/min.
Elongation at break:Refer to shift value of the sample in tension failure and former long ratio, as a percentage (%).
100% modulus:Refer to tensile strength when elongation is 100%.
Embodiment 1
Formula:(percentage by weight)
Preparation method:
(1) polytetrahydrofuran diol (Mn=2000), dimethylolpropionic acid, 2- methyl-1,3-propanediols are mixed to 80
DEG C, octoate catalyst stannous is added, 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to 80 DEG C, and both of the above is respectively through tooth
Take turns metering pump and flowmeter, by mixing head enter rotating speed for 250rpm, L/D=30, temperature be respectively 120 DEG C, 130 DEG C, 140
DEG C, 150 DEG C, 150 DEG C, 160 DEG C, the reaction of 210 DEG C of double-screw reactor, residence time 0.5min;
(2) be 150 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 150 DEG C,
Pressure is 0.5Mpa, concentration is that 1.6%wt triethylamine aqueous solutions are also injected into shear pump, shears 4min;
(3) it is collected into stainless steel storage tank after heat exchanger is cooled to 30 DEG C, is depressured normal pressure, is stirred after collecting completely
5min, you can obtain the aqueous polyurethane dispersion, solid content 30.0%wt.Product characters are observed, have not been found
Undissolved White Flocculus, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 2
Formula:(mass percent)
Preparation method:
(1) polytetrahydrofuran diol (Mn=2000), dihydromethyl propionic acid, 1,4-butanediol are mixed to 60 DEG C, added
Catalyst zinc Isoocatanoate, toluene di-isocyanate(TDI) (TDI) are warming up to 60 DEG C, and both of the above is respectively through gear wheel metering pump and flow
Meter, by mixing head inject rotating speed for 200rpm, L/D=56, temperature be respectively 80 DEG C, 100 DEG C, 130 DEG C, 140 DEG C, 150 DEG C,
170 DEG C, 215 DEG C of double-screw reactor reaction, residence time 2min;
(2) be 120 DEG C through smelt gear pump implantation temperature, rotating speed be in 1000rpm shear pumps, while temperature be 120 DEG C,
Pressure is that 0.2Mpa concentration is that 2.1%wt triethylamine aqueous solutions are also injected into shear pump, shears 5min;
(3) 50 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
10min, it is possible to obtain the aqueous polyurethane dispersion, solid content 35.7%wt.Product characters are observed, are not found
There is undissolved White Flocculus, emulsion-stabilizing is homogeneous.After standing one month, do not precipitate.
Embodiment 3
Formula:(percentage by weight)
Preparation method:
(1) polytetrahydrofuran diol (Mn=2000), dimethylolpropionic acid, 2- methyl-1,3-propanediols are mixed to 80
DEG C, octoate catalyst stannous is added, 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to 80 DEG C, and both of the above is respectively through tooth
Take turns metering pump and flowmeter, by mixing head inject rotating speed for 250rpm, L/D=40, temperature be respectively 120 DEG C, 120 DEG C, 130
DEG C, 140 DEG C, 150 DEG C, 170 DEG C, the reaction of 215 DEG C of double-screw reactor, residence time 1min;
(2) be 150 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 150 DEG C,
Pressure is 0.5Mpa, concentration is that 1.4%wt triethylamine aqueous solutions are also injected into shear pump, high speed shear 4min;
(3) it is collected into stainless steel storage tank after heat exchanger is cooled to 30 DEG C, is depressured normal pressure, is stirred after collecting completely
5min, you can obtain the aqueous polyurethane dispersion, solid content 30.0%wt.Product characters are observed, have not been found
Undissolved White Flocculus, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 4
Formula:(mass percent)
Preparation method:
(1) by polypropylene oxide ethylene oxide copolymerization dihydric alcohol (Mn=2000), dimethylolpropionic acid, 1,3 butylene glycol with
Quality 88.20%, 6.50%, 5.3% are mixed and heated to 90 DEG C, add catalyst isooctyl acid bismuth, 4,4- diphenyl-methane, two isocyanide
Acid esters (MDI) is warming up to 90 DEG C, and respectively through gear wheel metering pump and flowmeter, inject rotating speed by mixing head is both of the above
250rpm, L/D=50, temperature are respectively 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 150 DEG C, 160 DEG C, 210 DEG C of twin-screw it is anti-
Device is answered to react, residence time 1.5min;
(2) be 180 DEG C through smelt gear pump implantation temperature, rotating speed be in 3000rpm shear pumps, while temperature be 180 DEG C,
Pressure is 1.3Mpa, concentration is that 2.8%wtN- methyl diethanolamine aqueous solutions are also injected into shear pump, shears 3min;
(3) 40 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
15min, you can obtain the aqueous polyurethane dispersion, solid content 41.7%wt.Product characters are observed, have not been found
Undissolved White Flocculus, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 5
Formula:(mass percent)
Preparation method:
(1) by poly- ethylene carbonate esterdiol (Mn=2000), polytetrahydrofuran diol (Mn=2000), dihydroxymethyl third
Acid, neopentyl glycol are mixed to 100 DEG C, add octoate catalyst stannous, and hydrogenation 4,4- '-diphenylmethane diisocyanates (HMDI) rise
Temperature to 90 DEG C, both of the above respectively through gear wheel metering pump, flowmeter, by mixing head inject rotating speed for 300rpm, L/D=16,
Temperature is respectively 130 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 205 DEG C of double-screw reactor reaction, during stop
Between be 2min;
(2) be 150 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 150 DEG C,
Pressure is 0.5Mpa, concentration is that 4.0%wt triethanolamine aqueous solutions are also injected into shear pump, shears 4min;
(3) 30 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
8min, you can obtain the aqueous polyurethane dispersion, solid content 46.4%wt.Product characters are observed, have not been found
Undissolved White Flocculus, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 6
Formula:(mass percent)
Preparation method:
(1) polytetrahydrofuran diol (Mn=2000), dihydromethyl propionic acid, ethylene glycol are mixed to 80 DEG C, addition catalysis
Agent dibutyl tin laurate, molar ratio 1:1 4,4- '-diphenylmethane diisocyanates (MDI) and isophorone diisocyanate
Ester (IPDI) is warming up to 80 DEG C, and both of the above through gear wheel metering pump, flowmeter, is respectively by injecting rotating speed after mixing head
250rpm, L/D=40, temperature are respectively 120 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 170 DEG C, 215 DEG C of twin-screw it is anti-
Device is answered to react, residence time 2.5min;
(2) be 120 DEG C through smelt gear pump implantation temperature, rotating speed be in 2000rpm shear pumps, while temperature be 120 DEG C,
Pressure is that 0.2Mpa concentration is that 1.9%wt triethylamine aqueous solutions are also injected into shear pump, shears 5min;
(3) 40 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
15min, it is possible to obtain the aqueous polyurethane dispersion, solid content 35.3%wt.Product characters are observed, are not found
There is undissolved White Flocculus, emulsion-stabilizing is homogeneous.After standing one month, do not precipitate.
Embodiment 7
Formula:(mass percent)
Preparation method:
(1) by polypropylene oxide ethylene oxide copolymerization dihydric alcohol (Mn=2000), polytetrahydrofuran diol (Mn=2000),
Dihydromethyl propionic acid, 1,3-BDO are mixed to 60 DEG C, add catalyst zinc Isoocatanoate, molar ratio 1:1 4,4- hexichol first
Alkane diisocyanate (MDI) and isophorone diisocyanate (IPDI) are warming up to 60 DEG C, and both of the above is respectively through metering gear
Pump, flowmeter, by mixing head inject rotating speed for 200rpm, L/D=50, temperature be respectively 80 DEG C, 100 DEG C, 130 DEG C, 140
DEG C, 150 DEG C, 170 DEG C, the reaction of 215 DEG C of double-screw reactor, residence time 3min;
(2) be 180 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 180 DEG C,
Pressure is 1.3Mpa, concentration 2.7%wtN, N- aqueous dimethylethanolamine is also injected into shear pump, shears 3min;
(3) 40 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
5min, you can obtain the aqueous polyurethane dispersion, solid content 41.6%wt.Product characters are observed, have not been found
Undissolved White Flocculus, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 8
Formula:(mass percent)
Preparation method:
(1) poly- ethylene carbonate esterdiol (Mn=2000), dimethylolpropionic acid, neopentyl glycol are mixed to 100 DEG C, added
Add catalyst isooctyl acid bismuth, hexamethylene diisocyanate (HDI) is warming up to 100 DEG C, both of the above respectively through gear wheel metering pump,
Flowmeter, by mixing head inject rotating speed for 300rpm, L/D=20, temperature be respectively 130 DEG C, 130 DEG C, 140 DEG C, 150 DEG C,
150 DEG C, 150 DEG C, 205 DEG C of double-screw reactor reaction, residence time 3min;
(2) be 150 DEG C by smelt gear pump implantation temperature, rotating speed be that while temperature is 150 in 1500rpm shear pumps
DEG C, pressure 0.5Mpa, concentration be that 4.0%wt diethanol amine aqueous solutions are also injected into shear pump, shear 4min;
(3) 30 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
15min, you can obtain the aqueous polyurethane dispersion, solid content 50.0%wt.Product characters are observed, have not been found
Undissolved White Flocculus, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 9
Formula:(mass percent)
Preparation method:
(1) by polytetramethylene carbonate diol glycol (Mn=500), Polyoxypropylene diol (Mn=10000), dihydroxymethyl
Propionic acid, 1,6- hexylene glycols are mixed and heated to 100 DEG C, add catalyst isooctyl acid bismuth, hexamethylene diisocyanate (HDI) heating
To 100 DEG C, both of the above through gear wheel metering pump, flowmeter, injects rotating speed for 300rpm, L/D=50, temperature by mixing head respectively
Respectively 100 DEG C of degree, 120 DEG C, 130 DEG C, 140 DEG C, 170 DEG C, 200 DEG C, 230 DEG C of double-screw reactor reaction, residence time
3min;
(2) be 150 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 150 DEG C,
Pressure is 0.5Mpa, concentration is that 2.3%wt triethylamine aqueous solutions are also injected into shear pump, shears 4min;
(3) 30 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
5min, you can obtain the aqueous polyurethane dispersion, solid content 40%wt.Product characters are observed, have not been found not
The White Flocculus of dissolving, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 10
Formula:(mass percent)
Preparation method:
(1) by polyadipate -1,6-HD esterdiol (Mn=2000), polyneopentyl glycol adipate glycol (Mn=
2000), dihydromethyl propionic acid, 1,3-BDO are mixed and heated to 110 DEG C, add catalyst zinc Isoocatanoate, molar ratio 1:1
4,4- '-diphenylmethane diisocyanates (MDI) and paraphenylene diisocyanate (PPDI) are warming up to 110 DEG C, and both of the above is respectively through tooth
Take turns metering pump, flowmeter, by mixing head inject rotating speed for 300rpm, L/D=20, temperature be respectively 130 DEG C, 130 DEG C, 140
DEG C, 150 DEG C, 150 DEG C, 150 DEG C, the reaction of 205 DEG C of double-screw reactor, residence time 3min;
(2) be 180 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 180 DEG C,
Pressure is 1.3Mpa, concentration is that 1.94%wt triethylamine aqueous solutions are also injected into shear pump, shears 3min;
(3) 40 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
5min, you can obtain the aqueous polyurethane dispersion, solid content 35.3%wt.Product characters are observed, have not been found
Undissolved White Flocculus, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 11
Formula:(mass percent)
Preparation method:
(1) by poly- neopentyl glycol carbonate esterdiol (Mn=4000), PolyTHF dihydric alcohol (Mn=2000), dihydroxymethyl
Propionic acid, 1,4-butanediol are mixed to 120 DEG C, add catalyst isooctyl acid bismuth, molar ratio 3:2 hydrogenation 4,4- diphenyl-methanes two
Isocyanates (HMDI) and hexamethylene diisocyanate (HDI) are warming up to 120 DEG C, both of the above respectively through gear wheel metering pump,
Flowmeter by injecting rotating speed after mixing head for 2500rpm, L/D=30, temperature is respectively 130 DEG C, 130 DEG C, 140 DEG C, 150
DEG C, 150 DEG C, 150 DEG C, the reaction of 205 DEG C of double-screw reactor, residence time 3min;
(2) be 150 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 150 DEG C,
Pressure is 0.5Mpa, concentration is that 0.45%wt sodium hydrate aqueous solutions are also injected into shear pump, shears 4min;
(3) 30 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
10min, you can obtain the aqueous polyurethane dispersion, solid content 30%wt.Product characters are observed, have not been found not
The White Flocculus of dissolving, emulsion-stabilizing are homogeneous.After standing one month, do not precipitate.
Embodiment 12
Formula:(mass percent)
Preparation method:
(1) by polyoxyethylene glycol (Mn=500), polyadipate -1,4- butyl glycol ester diols (Mn=4000), two
Hydroxymethyl propionic acid, 1,4-butanediol are mixed and heated to 90 DEG C, add octoate catalyst stannous, and toluene di-isocyanate(TDI) (TDI) rises
For temperature to 90 DEG C, both of the above is respectively 250rpm, L/D=by injecting rotating speed after mixing head through gear wheel metering pump, flowmeter
30th, temperature is respectively 120 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 170 DEG C, 215 DEG C of double-screw reactor reaction, is stopped
Time 3min;
(2) be 120 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 120 DEG C,
Pressure is that 0.2Mpa concentration is that 2.0%wtN- methyl diethanolamine aqueous solutions are also injected into shear pump, shears 5min;
(3) 50 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, collect it is full after stir
10min, you can obtain the aqueous polyurethane dispersion, solid content 36.6%wt.
Product characters are observed, have not found undissolved White Flocculus, emulsion-stabilizing is homogeneous.After standing one month,
Do not precipitate.
Comparative example 1
Formula:(mass percent)
Preparation method:
(1) polytetrahydrofuran diol (Mn=2000), dimethylolpropionic acid, 2- methyl-1,3-propanediols are mixed to 80
DEG C, octoate catalyst stannous is added, 4,4- '-diphenylmethane diisocyanates (MDI) are warming up to 80 DEG C, and both of the above is respectively through tooth
Take turns metering pump, flowmeter, by mixing head inject rotating speed for 250rpm, L/D=10, temperature be respectively 120 DEG C, 130 DEG C, 140
DEG C, 150 DEG C, 150 DEG C, 160 DEG C, the reaction of 210 DEG C of double-screw reactor, residence time 1min;
(2) be 150 DEG C through smelt gear pump implantation temperature, rotating speed be in 1500rpm shear pumps, while temperature be 150 DEG C,
Pressure is 0.5Mpa, concentration is that 1.6%wt triethylamine aqueous solutions are also injected into shear pump, shears 4min;
(3) it is collected into stainless steel storage tank after heat exchanger is cooled to 30 DEG C, is depressured normal pressure, is stirred after collecting completely
5min;The aqueous polyurethane dispersion that solid content is 30.0%wt can be obtained, testing result shows that stability is bad, stands
Two days later, there are a large amount of white precipitates.
Comparative example 2
Formula:(mass percent)
Preparation method:
(1) polytetrahydrofuran diol (Mn=2000), dihydromethyl propionic acid, 1,4-butanediol are mixed and heated to 60 DEG C,
Catalyst zinc Isoocatanoate is added, toluene di-isocyanate(TDI) (TDI) is warming up to 60 DEG C, and both of the above is respectively through gear wheel metering pump, stream
Gauge by injecting rotating speed after mixing head for 200rpm, L/D=70, temperature is respectively 80 DEG C, 100 DEG C, 130 DEG C, 140 DEG C,
150 DEG C, 170 DEG C, 215 DEG C of double-screw reactor reaction, residence time 3min;
(2) be 120 DEG C through smelt gear pump implantation temperature, rotating speed be in 1000rpm shear pumps, while temperature be 120 DEG C,
Pressure is that 0.2Mpa concentration is that 2.1%wt triethylamine aqueous solutions are also injected into shear pump, shears 5min;
(3) 50 DEG C are cooled to through heat exchanger, are depressurized to normal pressure and are collected into stainless steel storage tank, observe product characters, hair
Existing a large amount of undissolved White Flocculus, can not obtain the lotion of stable uniform.
The physical property of aqueous polyurethane dispersion obtained by embodiment 1-12 such as table:
Shown by the testing result of the heat exchange comparative example of the above embodiments 1~12:
Since the double-screw reactor of the present invention has used special draw ratio, suitable temperature and time, ensureing original
Material reduces the generation of side reaction as far as possible again while the reaction was complete, the WTPUD lotion storage stabilities being prepared are good
Well, performance is stablized excellent, can be widely applied to the every field such as synthetic leather, adhesive, coating, fabric coating, finishing agent, especially
Be used as synthetic leather resin, can be applied to base fabric bottom material resin, surface layer resin, tie layer resins, intermediate layer resin, foaming layer tree
The fields such as fat.
Claims (10)
1. the preparation method of the solvent-free aqueous polyurethane dispersion of continous way, it is characterised in that include the following steps:
(1) by polymer diatomic alcohol, diisocyanate, small molecule dihydric alcohol, two terminal hydroxy group Y-shaped pendant hydrophilic chain extension of low melting point
Agent and catalyst, are preheated to 60-100 DEG C respectively, after being then input to mixer disperses mixing, are input in double-screw reactor
Reaction, obtains polyurethane melt;
(2) by the polyurethane melt of acquisition, it is continuously injected into shear pump, while water or water with neutralizer is injected into shearing
Pump, and disperse in 120-200 DEG C of high temperature and 0.2-1.5Mpa down cuts, obtain aqueous polyurethane dispersion;
(3) aqueous polyurethane dispersion of gained, decrease temperature and pressure, the solvent-free aqueous polyurethane stirred are disperseed
Body.
2. according to the method described in claim 1, it is characterized in that, using 16≤L/D≤56, more than rotating speed 200-300rpm
Double screw extruder, wherein:L represents spiro rod length, and D represents screw diameter, in the double-screw reactor, reaction temperature point
For 7 sections, first segment is 80-130 DEG C, and second segment is 100-130 DEG C, and the 3rd section is 130-140 DEG C, and the 4th section is 140-150 DEG C,
5th section is 150-170 DEG C, and the 6th section is 150-200 DEG C, and the 7th section is 205-230 DEG C, during stop of the material in twin-screw
Between be 0.5-3min.
3. according to the method described in claim 1, it is characterized in that, the polymer diatomic alcohol is polyether Glycols, polyester
Dihydric alcohol, one or more mixtures in polycarbonate glycol;
The polyether Glycols use 2 terminal hydroxy groups, and number-average molecular weight is the polyether oligomer of 200-10000, including is not limited to:
PolyTHF dihydric alcohol (PTMEG), Polyoxypropylene diol (PPG), polyoxyethylene glycol (PEG) and polyoxygenated third
One or more mixtures of alkene ethylene oxide copolymerization dihydric alcohol (PEPG);
The polyester diol is to contain 2 oligomers of the terminal hydroxy group containing polyester construction, range of number-average molecular weight 200-4000,
Including being not limited to:The butyl glycol ester diol of polyadipate -1,4 (PBA), polyethylene glycol adipate glycol (PEA), polyadipate third
It is glycol esterdiol (PPA), the hexylene glycol of polyadipate -1,6 esterdiol (PHA), polyneopentyl glycol adipate glycol (PNA), poly-
Adipate glycol butyl glycol ester diol (PEBA), polyadipate ethylene glycol propylene glycol ester glycol (PEPA), polyadipate oneself two
Alcohol neopentyl glycol esterdiol (PHNA), polybutyleneadipate hexylene glycol esterdiol (PBHA), polybutyleneadipate new penta 2
Alcohol esterdiol (PBNA), the one or more mixing for gathering own Inner esterdiols;
The polycarbonate glycol uses the oligomer containing 2 terminal hydroxy group carbonate-containing structures, range of number-average molecular weight
For 200-4000, exchanged and synthesized with binary alcohol esters by carbonic diester, including be not limited to:Poly- carbonic acid hexylene glycol esterdiol, poly- carbonic acid
One or more mixtures of pentadiol ester glycol, polytetramethylene carbonate diol glycol, poly (propylene carbonate) glycol etc..
4. according to the method described in claim 1, it is characterized in that, the diisocyanate is different selected from 4,4- diphenyl-methanes two
Cyanate (MDI), toluene di-isocyanate(TDI) (TDI), tolylene diisocyanate (XDI), 1,5- how diisocyanate
(NDI), paraphenylene diisocyanate (PPDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI),
Hydrogenate the mixture of one kind or any combination in 4,4- '-diphenylmethane diisocyanates (HMDI).
5. according to the method described in claim 1, it is characterized in that, the small molecule dihydric alcohol is selected from ethylene glycol, 1,2- third
Glycol, 1,3- propane diols, 1,4- butanediols, 1,3 butylene glycol, 1,5- pentanediols, neopentyl glycol, 1,6-HD, 1,8- pungent two
One or more kinds of mixtures in alcohol, hydroquinone hydroxyethyl ether (HQEE), cyclohexane dimethanol, 2- methyl-1,3-propanediols.
6. according to the method described in claim 1, it is characterized in that, the two terminal hydroxy group Y-shaped pendant hydrophilic of low melting point expands
Chain agent, is one kind or mixture in dihydromethyl propionic acid and dimethylolpropionic acid.
7. according to the method described in claim 1, it is characterized in that, the catalyst is stannous octoate, two fourth of tin dilaurate
One or more in Ji Xi, organic zinc, organo-bismuth.
8. according to claim 1~7 any one of them method, it is characterised in that the solvent-free aqueous polyurethane disperses
Body, includes the component of following mass percent:
9. the aqueous polyurethane dispersion prepared according to claim 1~8 any one of them method.
10. the application of aqueous polyurethane dispersion according to claim 9, it is characterised in that for synthetic leather, gluing
Agent, coating, fabric coating, finishing agent, base fabric bottom material resin, surface layer resin, tie layer resins, intermediate layer resin or foaming layer tree
Fat.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711045576.XA CN107903376A (en) | 2017-10-31 | 2017-10-31 | Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711045576.XA CN107903376A (en) | 2017-10-31 | 2017-10-31 | Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107903376A true CN107903376A (en) | 2018-04-13 |
Family
ID=61842998
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711045576.XA Pending CN107903376A (en) | 2017-10-31 | 2017-10-31 | Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107903376A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109535377A (en) * | 2018-12-04 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of aqueous polyurethane and the preparation method and application thereof with from foam stabilizing function |
CN109734866A (en) * | 2018-12-13 | 2019-05-10 | 华南理工大学 | A kind of high-performance anionic and nonionic type aqueous polyurethane dispersion and preparation method thereof |
CN110862509A (en) * | 2019-11-29 | 2020-03-06 | 山东天庆科技发展有限公司 | Water-based solvent-free polyurethane resin and preparation method thereof |
WO2022183604A1 (en) * | 2021-03-03 | 2022-09-09 | 四川大学 | Method for completely continuously preparing waterborne polyurethane by means of prepolymerization-emulsification |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102336881A (en) * | 2011-07-08 | 2012-02-01 | 华南理工大学 | Polyurethane ionic polymer and preparation method of dispersoid adhesive thereof |
CN102633971A (en) * | 2012-04-19 | 2012-08-15 | 王武生 | Double-screw reactor design based continuous production process of aqueous polyurethane dispersion |
CN103382253A (en) * | 2013-06-25 | 2013-11-06 | 上海华峰新材料研发科技有限公司 | Waterborne polyurethane dispersion with high performance and preparation method thereof |
CN105440240A (en) * | 2015-12-04 | 2016-03-30 | 上海华峰材料科技研究院(有限合伙) | Continuous production method for preparing waterborne polyurethane ionomer and dispersoid of waterborne polyurethane ionomer |
-
2017
- 2017-10-31 CN CN201711045576.XA patent/CN107903376A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102336881A (en) * | 2011-07-08 | 2012-02-01 | 华南理工大学 | Polyurethane ionic polymer and preparation method of dispersoid adhesive thereof |
CN102633971A (en) * | 2012-04-19 | 2012-08-15 | 王武生 | Double-screw reactor design based continuous production process of aqueous polyurethane dispersion |
CN103382253A (en) * | 2013-06-25 | 2013-11-06 | 上海华峰新材料研发科技有限公司 | Waterborne polyurethane dispersion with high performance and preparation method thereof |
CN105440240A (en) * | 2015-12-04 | 2016-03-30 | 上海华峰材料科技研究院(有限合伙) | Continuous production method for preparing waterborne polyurethane ionomer and dispersoid of waterborne polyurethane ionomer |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109535377A (en) * | 2018-12-04 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of aqueous polyurethane and the preparation method and application thereof with from foam stabilizing function |
CN109535377B (en) * | 2018-12-04 | 2021-04-23 | 山东天庆科技发展有限公司 | Waterborne polyurethane with self-foam stabilizing function and preparation method and application thereof |
CN109734866A (en) * | 2018-12-13 | 2019-05-10 | 华南理工大学 | A kind of high-performance anionic and nonionic type aqueous polyurethane dispersion and preparation method thereof |
CN110862509A (en) * | 2019-11-29 | 2020-03-06 | 山东天庆科技发展有限公司 | Water-based solvent-free polyurethane resin and preparation method thereof |
WO2022183604A1 (en) * | 2021-03-03 | 2022-09-09 | 四川大学 | Method for completely continuously preparing waterborne polyurethane by means of prepolymerization-emulsification |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107840937A (en) | Solvent-free aqueous polyurethane dispersion of extrusion molding and its preparation method and application | |
CN107903377A (en) | Solvent-free sulfonate aqueous polyurethane dispersion of continous way and preparation method thereof | |
CN105062403B (en) | Synthetic leather adhesive and preparation method | |
CN107903376A (en) | Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application | |
CN102333805B (en) | Aqueous polyurethane resin dispersion and manufacturing method thereof | |
CN101585903B (en) | Water-borne polyurethane and preparation method thereof | |
CN103382253B (en) | A kind of high-performance water-based polyurethane dispersoid and preparation method thereof | |
CN102532463B (en) | Aqueous polyurethane and preparation method thereof | |
CN105440240B (en) | Prepare the continuous production method of aqueous polyurethane ionomer and its dispersion | |
CN102459383B (en) | For the production of the solvent of polyurethane dispersions | |
CN107522841A (en) | A kind of method that solventless method prepares carboxylic acid/sulfonic acid mixed type high-solid content water-based polyurethane | |
CN108097194B (en) | Continuous production system for preparing aqueous polyurethane dispersion, continuous production process for aqueous polyurethane dispersion and application | |
CN102702471A (en) | Method for preparing solvent-free aqueous polyurethane dispersion | |
CN104530370A (en) | Solvent-free method for preparing non-ionic water-borne polyurethane | |
CN107022297A (en) | A kind of water-fast aqueous polyurethane coating with bi component and preparation method thereof | |
CN108264622B (en) | Waterborne polyurethane, preparation intermediate and preparation method thereof | |
CN102858847B (en) | Polyether polyols and urethane resin and containing these coating agent | |
CN107964104A (en) | Solvent-free aqueous polyurethane dispersion and its preparation method and application | |
CN107849208A (en) | Method and apparatus for continuous production aqueous polyurethane dispersion | |
EP2185618A1 (en) | Process for the production of hyperbranched, dendritic polyurethanes by means of reactive extrusion | |
CN109868516A (en) | A kind of production method of melt spun spandex polyurethane cross-linking agent | |
WO2021023750A1 (en) | Method for producing thermoplastically processable polyurethane polymers | |
JP4976249B2 (en) | Method for producing aqueous polyurethane resin | |
CN104087235A (en) | Water-based polyurethane adhesive and preparation method thereof | |
CN105980431A (en) | Aqueous urethane-urea resin composition and production method, and, reactive emulsifier and emulsification method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180413 |