CN108017738A - A kind of environment-friendly water-based compound terminator - Google Patents
A kind of environment-friendly water-based compound terminator Download PDFInfo
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- CN108017738A CN108017738A CN201711226175.4A CN201711226175A CN108017738A CN 108017738 A CN108017738 A CN 108017738A CN 201711226175 A CN201711226175 A CN 201711226175A CN 108017738 A CN108017738 A CN 108017738A
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- terminator
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- based compound
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- isopropylhydroxyla
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Polymerisation Methods In General (AREA)
Abstract
A kind of environment-friendly water-based compound terminator and preparation method thereof, include isopropylhydroxyla, diethyl hydroxylamine and sodium perchlorate, deionized water is added in a kettle, sodium perchlorate is added in deionized water, isopropylhydroxyla, diethyl hydroxylamine or the mixture of the two are added after potassium hyperchlorate dissolving, is discharged after mixing.The environment-friendly water-based compound terminator of one kind of the present invention, reaction can be timely terminated when polymerisation reaches certain conversion ratio, the whiteness and ageing whiteness of synthesis polyvinyl chloride resin product can be improved at the same time, and the preparation method of the terminator has the characteristics that simple production process, raw material are easy to get, product use cost is low, easy to industrial application.
Description
Technical field
The present invention relates to technical field of fine, more particularly to a kind of environment-friendly water-based compound terminator.
Background technology
Aqueous suspension polymerization be synthesize polyvinyl chloride resin main method, in water solution system add dispersant, buffer,
The auxiliary agents such as initiator, pH adjusting agent and vinyl chloride monomer reaction raw materials, reactant high degree of dispersion is made under the action of stirring and
As stable lotion, protecting colloid in water by vinyl chloride monomer dispersion in small drop, each drop equivalent to
One polymerization system, the initiator for being dissolved in monomer resolve into free radical at the polymerization temperature, trigger the polymerization of vinyl chloride monomer, whole
A polymerization process includes the unit processes such as chain initiation, chain growth, chain termination.
Chain initiation is the reaction that monomer forms free radical activity center, generally includes decomposition of initiator and forms primary group of free radicals
R；Primary group of free radicals and VCM additions, form monomer radical CH2Two steps of C HCI；The chain growth stage is to trigger to be formed in chain
On the basis of monomer radical, continuous addition monomer molecule makes chain growth form macromolecular；Termination step includes free radical phase
Interaction and terminate, the living chain free radicals interaction of two growths and make chain termination, therefore the termination of radical polymerization is anti-
It should be bimolecular reaction, there is two kinds of forms of coupling and disproportionation.Polymerization process late monomer concentration is relatively low, if by reaction certainly
It is dynamic to terminate, then terminated and occupied an leading position with biradical disproportionation, two big PVC free radical molecules meet to form a saturation macromolecular
And terminate；Another is then the unsaturated termination with double bond, as a result causes generated small molecule quality PVC, with side chain
PVC, the PVC products with allyl chloride structure increase.PVC heat endurances with this molecular structure are very poor, especially divide
There are allyl chloride in subchain, there is height activity, be easy to dehydrochlorination in the case of heated, shape conjugated polyene structure,
The HCl of starting stage abjection becomes the catalyst that PVC macromolecular chain continues thermal decomposition, therefore, the reaction of dehydrochlorination again
Once will further to react becomes more easy, causes polyvinyl chloride resin product that heat ageing, yellow index increase occurs
Whiteness reduces.In addition under the action of heat or light, the homolysis of C-Cl keys occurs and generates high molecular free radical R；Due to free radical
Reaction activity, can carry out it is intermolecular or intramolecular further reaction to obtain stabilization, especially in aerobic existing feelings
Under condition, it is easy to the oxidation reaction of free radical, generation oxyradical RO, peroxylradicals ROO occurs；So as to further promote
Into the molecule cross-link of polyvinyl chloride, polyvinyl chloride aging had both been caused to occur.For that purpose it is necessary to reach setting in polymerisation
Terminator is initially added into during terminal, polymerisation terminal is about selected during conversion ratio 70-85%, in order to improve PVC products
For stability, it is necessary to eliminate the free radical and residual initiators remained in resin, this is also the weight for designing terminator compositing formula
Will foundation, good terminator can be rapidly remaining initiator, primary group of free radicals, monomer radical, the activity increased in kettle
Chain radical termination, inactivation, make undesirable reflex action stop immediately, good have stability PVC molecule knots to obtain
Structure.
The raw material of common terminator there are it is certain the defects of, such as：Bisphenol-A is a kind of more satisfactory polymerization terminator, is added
Although it is low very slow to enter kettle pressure drop after bisphenol-A, it was verified that yield does not have significant change, reacts basic and stop, while product
Hot property be significantly improved, but whiteness is slightly decreased.Acetone contracting amido thiocarbamide（ATSC）It is anti-compared with the polymerization of bisphenol-A Quick stop
Should, and thoroughly.But its effect is single, only play termination and without heat stabilization, and higher price.
Use the terminator formed through a variety of antioxidant compounding based on ATSC, such as Chinese patent
CN101921354A, CN101735357A, CN1657546A, CN1654486A etc., however it remains of high cost and use toxicity
The problems such as larger ATSC materials.In addition, also there is other kinds of terminator, such as：Chinese patent CN1649913A discloses one
The chain termination method of kind PVC polymerizations, wherein being complex as terminator with phenolic antioxidant with free nitroxyl.Chinese patent
In the method for vinyl chloride aqueous suspension polymerization disclosed in CN1501945A, use nitroxide type stable free radical whole as polymerization
Only agent, or the compound of nitroxide type stable free radical material and diethyl hydroxylamine are terminator.Chinese patent
CN201110380532.9 discloses a kind of preparation method of polyvinyl chloride resin terminator, with 2,6- di-t-butyls -4-（1- benzene
Base ethyl）Phenol is the antioxidant product of principal product, adds organic solvent, is sufficiently stirred, and is constructed to meet mobility requirement
Liquid antioxidant product, then it is compound with functional antioxidant, a kind of oil-soluble, compound, liquid terminator product is made.This is several
Or terminator disclosed in a patent equally exist preparation process complexity, or it is of high cost the shortcomings of.
The content of the invention
First purpose of the present invention is, in place of overcome the deficiencies in the prior art, there is provided a kind of environment-friendly water-based compound
Terminator, can timely terminate reaction when polymerisation reaches certain conversion ratio, while can improve synthesis polyvinyl chloride resin production
The whiteness and ageing whiteness of product.
Second object of the present invention is, there is provided the preparation method of above-mentioned environment-friendly water-based compound terminator, this method
Have the characteristics that simple production process, raw material are easy to get, product use cost is low, easy to industrial application.
The environment-friendly water-based compound terminator of one kind of the present invention, includes isopropylhydroxyla, diethyl hydroxylamine and height
Sodium chlorate, the isopropylhydroxyla concentration are 15%, its mass parts is 80-100 parts, and the mass parts of diethyl hydroxylamine are 0-15
Part, the mass parts of sodium perchlorate are 5-20 parts, by deionized water by above-mentioned isopropylhydroxyla, diethyl hydroxylamine and sodium perchlorate
It is uniformly mixed, the mass parts of the deionized water are 50-83 parts.
Further, used diethyl hydroxylamine content is 85% or 98%.
Further, the mixing temperature is 25-35 DEG C.
A kind of preparation method of environment-friendly water-based compound terminator of the present invention, this method comprise the following steps that：
（1）Deionized water is added in a kettle；
（2）Deionized water in reaction kettle is heated, is warming up to 20-50 DEG C；
（3）Sodium perchlorate is added in deionized water after heating, isopropylhydroxyla, diethyl are added after potassium hyperchlorate dissolving
Azanol or the mixture of the two, discharge after mixing.
The environment-friendly water-based compound terminator of one kind of the present invention, can be when polymerisation reaches certain conversion ratio
Reaction is timely terminated, while the whiteness and ageing whiteness of synthesis polyvinyl chloride resin product can be improved, the preparation method tool of the terminator
There are simple production process, raw material to be easy to get, the characteristics of product use cost is low, easy to industrial application.
Embodiment
Embodiment 1：70 parts of deionized waters are first added in a kettle, are warming up to 25-30 DEG C, add 15 parts of sodium perchlorates,
100 part of 15% isopropylhydroxyla is added after to be dissolved, is discharged after mixing.
Embodiment 2：70 parts of deionized waters are first added in a kettle, are warming up to 25-30 DEG C, add 15 parts of sodium perchlorates,
60 part of 15% isopropylhydroxyla is added after to be dissolved, 6 part of 98% diethyl hydroxylamine, discharges after mixing.
Embodiment 3：70 parts of deionized waters are first added in a kettle, are warming up to 25-30 DEG C, add 15 parts of sodium perchlorates,
40 part of 15% isopropylhydroxyla is added after to be dissolved, 9 part of 98% diethyl hydroxylamine, discharges after mixing.
Embodiment 4：70 parts of deionized waters are first added in a kettle, are warming up to 25-30 DEG C, add 15 parts of sodium perchlorates,
Added after to be dissolved, 16 part of 98% diethyl hydroxylamine, discharges after mixing.
The effect assessment experiment of the present invention and result：The PVC as made from for transparent boardy product etc. by suspension polymerization
Manufacturing condition, when polymerase 17 is small at 57 DEG C respectively, then takes polymerization material to be dried ten minutes at 160 DEG C, then pressed with whiteness instrument
GB/T 15595-2008 survey whiteness, and experimental result is as follows：
From the point of view of ageing whiteness, terminator of the embodiment of the present invention is added, all embodiment ageing whiteness of ageing whiteness are 85.1-
89.2, it is all higher than national standard high-class product index 78%.From terminating in terms of effect, positive effect, is a kind of excellent PVC terminators.
The basic principle and main feature of the present invention has been shown and described above.It should be understood by those skilled in the art that
The present invention is not limited to the above embodiments, and the above embodiments and description only illustrate the principle of the present invention,
Without departing from the spirit and scope, various changes and modifications of the present invention are possible, these changes and improvements all fall
Enter in claimed this reality invention scope.The claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (4)
1. a kind of environment-friendly water-based compound terminator, includes isopropylhydroxyla, diethyl hydroxylamine and sodium perchlorate, its feature exists
In：The isopropylhydroxyla concentration is 15%, its mass parts is 80-100 parts, and the mass parts of diethyl hydroxylamine are 0-15 parts, high
The mass parts of sodium chlorate are 5-20 parts, are mixed above-mentioned isopropylhydroxyla, diethyl hydroxylamine and sodium perchlorate by deionized water
Uniformly, the mass parts of the deionized water are 50-83 parts.
2. the environment-friendly water-based compound terminator of one kind according to claim 1, it is characterised in that：Used diethyl hydroxyl
Amine content is 85% or 98%.
3. the environment-friendly water-based compound terminator of one kind according to claim 1, it is characterised in that：The mixing temperature is
25-35℃。
4. the environment-friendly water-based compound terminator of one kind according to claim 1, it is characterised in that：The preparation of above-mentioned terminator
It is following steps that method, which includes,：
（1）Deionized water is added in a kettle；
（2）Deionized water in reaction kettle is heated, is warming up to 20-50 DEG C；
（3）Sodium perchlorate is added in deionized water after heating, isopropylhydroxyla, diethyl are added after potassium hyperchlorate dissolving
Azanol or the mixture of the two, discharge after mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711226175.4A CN108017738B (en) | 2017-11-29 | 2017-11-29 | Environment-friendly aqueous composite terminator |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711226175.4A CN108017738B (en) | 2017-11-29 | 2017-11-29 | Environment-friendly aqueous composite terminator |
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| CN108017738A true CN108017738A (en) | 2018-05-11 |
| CN108017738B CN108017738B (en) | 2020-03-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112830986A (en) * | 2020-12-27 | 2021-05-25 | 新沂市星辰新材料科技有限公司 | PVC (polyvinyl chloride) terminator capable of improving whiteness and aged whiteness and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369512A (en) * | 2000-03-07 | 2002-09-18 | 阿托费纳化学股份有限公司 | Compsns. for fast stopping free radical emulsion polymerization and emlsion therefrom |
| CN103635496A (en) * | 2012-01-24 | 2014-03-12 | 阿肯马法国公司 | Process for preparing halogenated polymers |
-
2017
- 2017-11-29 CN CN201711226175.4A patent/CN108017738B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369512A (en) * | 2000-03-07 | 2002-09-18 | 阿托费纳化学股份有限公司 | Compsns. for fast stopping free radical emulsion polymerization and emlsion therefrom |
| CN103635496A (en) * | 2012-01-24 | 2014-03-12 | 阿肯马法国公司 | Process for preparing halogenated polymers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112830986A (en) * | 2020-12-27 | 2021-05-25 | 新沂市星辰新材料科技有限公司 | PVC (polyvinyl chloride) terminator capable of improving whiteness and aged whiteness and preparation method thereof |
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| CN108017738B (en) | 2020-03-31 |
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