CN1207318C - Process for producing castor oil modified polyarylester graft copolymer textile size and size - Google Patents
Process for producing castor oil modified polyarylester graft copolymer textile size and size Download PDFInfo
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- CN1207318C CN1207318C CN 03138724 CN03138724A CN1207318C CN 1207318 C CN1207318 C CN 1207318C CN 03138724 CN03138724 CN 03138724 CN 03138724 A CN03138724 A CN 03138724A CN 1207318 C CN1207318 C CN 1207318C
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- castor oil
- oil modified
- polyarylester
- graft copolymerization
- spinning sizing
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Abstract
The present invention provides a production method for castor oil modified polyarylester graft copolymerization textile sizing materials, which is characterized in that firstly, castor oil, phthalic anhydride (benzoic anhydride), maleic anhydride and polyethylene glycol are used as raw materials and are synthesized into new castor oil modified polyarylester through high-molecule polycondensation; secondly, graft-copolymerization emulsion is synthesized, the unsaturated double bond on the macromolecular chain of the modified polyarylester, acrylic and an acrylamide monomer have high-molecule graft copolymerization under the action of an initiator, and the castor oil modified polyarylester graft copolymerization textile sizing materials are obtained. The castor oil modified polyarylester graft copolymerization textile sizing materials produced in the method are characterized in that the sizing materials are high-concentration granules in an emulsion form or a powder form; the sizing materials have the advantages of strong adhesive power on hydrophobic chemical fibers and natural fibers, good water solubility, good flexibility, good compatibility with starch, and lower re-stickiness than that of acrylic sizing materials; the sizing materials overcome the defects in PVA.
Description
Technical field
The invention belongs to the making method and the slurry of spinning sizing agent, is a kind of making method and slurry of castor oil modified polyarylester graft copolymerization spinning sizing agent specifically.
Background technology
Up to now, the chemical sizwe of production and sales both at home and abroad is mainly polyvinyl alcohol (PVA) and polyacrylic acid and copolymer pulp thereof.In recent years, domestic also some producer declared to use the polyester slurry of import, but all failed to point out to contain in the molecular structure of this type of slurry the aromatic ring ester group with the polyster fibre molecular mimicry
United States Patent (USP) once described in detail with terylene waste modification processing can obtain water dispersible slurry and coating, and domestic data reported with raw materials such as terephthalic acids once and synthesize water-soluble Polyester Size for Warp Sizing that performance was near PVA.With regard to current synthetic spinning sizing agent, PVA and acrylic size at home and abroad are widely used, and from the analysis comparing result of use properties, PVA still belongs to first-selected synthetic slurry.The reasonably combined use of above-mentioned two big class synthetic slurries and natural starch slurry can be satisfied the sizing technique requirement of most of textile product.But the PVA slurry in the research field of spinning sizing agent, is being explored new synthetic chemistry slurry to replace PVA in recent years because it pollutes environment and self shortcomings such as the knot laitance coating on sizing technique, difficult leasing.Some developed countries of West Europe have forbidden PVA, and forbid containing the product import of PVA.China textile industry association clearly proposes " few with or without PVA " as the developing direction of slurry from now on.Therefore, market presses for the spinning sizing agent that a kind of functional and alternative PVA is provided.
Summary of the invention
The objective of the invention is shortcoming and defect, a kind of making method and slurry of castor oil modified polyarylester graft copolymerization spinning sizing agent is provided at prior art.Hydrophobicity chemical fibre and natural fiber all there are higher adhesive power, good water solubility, snappiness is good, and is good with the starch compatibility, and the viscosity ratio acrylic size greatly reduces again, overcomes the shortcoming of PVA.
The present invention seeks to be achieved through the following technical solutions: a kind of making method of castor oil modified polyarylester graft copolymerization spinning sizing agent, it is characterized in that: the first step, the synthetic method of castor oil modified unsaturated polyester aromatic ester, with Viscotrol C and phthalic anhydride and MALEIC ANHYDRIDE and polyoxyethylene glycol raw material, synthesize castor oil modified polyarylester through the polymer polycondensation; Second step, the synthetic method of grafted copolymerized emulsion, the unsaturated double-bond on the above-mentioned modification polyarylester macromolecular chain is under action of evocating, carry out macromolecular grafted copolyreaction with acrylic acid or the like and acrylamide monomer, draw castor oil modified polyarylester graft copolymerization spinning sizing agent.
The synthetic method of described castor oil modified unsaturated polyester aromatic ester drops into Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, Viscotrol C, polyoxyethylene glycol in the reactor, at pure N
2Protection is heated down, stirs, and the fs temperature control reacted 2 hours at 100 ℃ to 150 ℃; The subordinate phase temperature control is at 180 ℃ to 210 ℃, and the later stage suitably vacuumizes, and aquifer yield reaches about 95% of theoretical aquifer yield, obtains flaxen castor oil modified unsaturated polyester aromatic ester, cooling back discharging.
The synthetic method of described grafted copolymerized emulsion adds quantitative water, unsaturated polyester aromatic ester, vinylformic acid, acrylamide in the reactor, fully stirs, at pure N
2Protection drip down initiator, early stage temperature control 40 ℃ to 65 ℃ 2 hours, the later stage was warming up to 65 ℃ to 85 ℃, obtained the oyster white slurry through 2 hours, cooling back discharging.
Used graft copolymerization evocating agent is the redox initiation system that ammonium persulphate and sodium bisulfite are formed.
The synthetic method of described castor oil modified unsaturated polyester aromatic ester, prescription is:
The raw material consumption
Polyoxyethylene glycol 1.5-2.5 mole
Tetra hydro Phthalic anhydride 1.0-2.0 mole
MALEIC ANHYDRIDE 0.5-1.0 mole
Viscotrol C 100-120 gram
The vitriol oil is a small amount of
The synthetic method of described grafted copolymerized emulsion, prescription is:
The raw material consumption
Modification polyarylester 50 grams
Polyoxyethylene glycol 30 grams
Vinylformic acid 0.4-1 mole
Acrylamide 0.4-0.8 mole
Deionized water 200ml
(NH
4)
2S
2O
82% aqueous solution is an amount of
NaHSO
32% aqueous solution is an amount of
A kind of castor oil modified polyarylester graft copolymerization spinning sizing agent of making as stated above is characterized in that described slurry is emulsion or powdery granule.
The present invention compared with prior art has many advantages and positively effect:
1, with homemade fine Viscotrol C and lower chemical industry material phthalic anhydride and the raw materials such as MALEIC ANHYDRIDE and polyoxyethylene glycol of price, synthesize novel castor oil modified polyarylester through the polymer polycondensation: novelty of the present invention also is the unsaturated double-bond on the above-mentioned modification polyarylester macromolecular chain, under action of evocating, carry out macromolecular grafted copolyreaction with monomers such as acrylic acid or the like and acrylamides, the fabric size of gained, on chemical structure, contain a large amount of functional groups similar on its macromolecular chain to the textile fibres macromolecular structure, particularly contain the aromatic ring ester group identical and flexible polyester chain is arranged with the polyster fibre macromolecular structure, and contain carboxyl, all kinds of hydrophilic radicals such as hydroxyl and amide group, therefore, hydrophobicity chemical fibre and natural fiber all there is higher adhesive power.Good water solubility helps destarch, and snappiness is joined slurry fortunately and the time can be added less or non-refuelling fat, and the viscosity ratio acrylic size greatly reduces again, and environmental pollution is little, has overcome the shortcoming of PVA slurry.
2, synthetic slurry of the present invention and starch compatibility are good, belong to the more perfect fabric size of over-all properties in the current synthetic slurry, the starching requirement of the polyester yarn that can be adapted to have a large capacity and a wide range, pure polyster fibre and other fibers.
3, synthetic slurry of the present invention can be divided into two kinds of the milk sap of high density and powdery granules, can be scattered in the water rapidly through stirring in normal-temperature water.According to the sizing technique requirement of yarn with different and textiles, can make up and reduce sizing costs by using producer to finish slurry.
Embodiment
One, the synthetic method of castor oil modified unsaturated polyester aromatic ester
1, prescription:
The raw material consumption
Polyoxyethylene glycol (A) 1.5-2.5 mole
Tetra hydro Phthalic anhydride (B
1) the 1.0-2.0 mole
MALEIC ANHYDRIDE (B
2) the 0.5-1.0 mole
Viscotrol C (O) 100-120 gram
The vitriol oil is a small amount of
2, embodiment 1
Accurately take by weighing 350 gram A, 360 gram B
1, 70 gram B
2With 100 gram Viscotrol C, add in the reactor, stir logical N
2, add the 1ml vitriol oil, be warming up to 100 ℃ of reactions 1 hour at a slow speed, be warming up to 150 ℃ again, reacted 1 hour, be warming up to 200 ℃, reactant is proceeded the platform polyreaction that contracts of dewatering, through 2 hours, aquifer yield reached about 97% of theoretical value approximately, can suitably vacuumize in this stage, again through 1 hour, be cooled to room temperature, discharging gets faint yellow modification polyarylester I.
3, embodiment 2
Accurately take by weighing 300 gram A, 360 gram B
1, 70 gram B
2And 100 gram Viscotrol C, add in the reactor, stir logical N
2, add the 1ml vitriol oil, be warming up to 100 ℃, reacted 1 hour, be warming up to 150 ℃ again, reacted 1 hour.Reactant begins the polycondensation of dewatering, when aquifer yield reach theoretical value 50% the time, be warming up to 200 ℃-210 ℃, reacted 2 hours, aquifer yield reaches theoretical about 98%.Suitably vacuumize, reacted 1 hour again, be cooled to room temperature, discharging gets faint yellow modification polyarylester II:
4, embodiment 3
Accurately take by weighing 350 gram A, 360 gram B
1, 50 gram B
2With 100 gram Viscotrol C, other obtains faint yellow modification polyarylester III as embodiment 1.
5, embodiment 4
Accurately take by weighing 350 gram A, 360 gram B
1, 70 gram B
2With 120 gram Viscotrol C, other operating performances such as example 1: obtain the modification polyarylester IV that faint yellow flowability is better than embodiment 1, embodiment 2, embodiment 3.
6, embodiment 5
Accurately weighing 350 restrains A, 360 gram B
1, 70 gram B
2With 100 gram Viscotrol C, add in the reactor, add the 1ml vitriol oil, be warming up to 150 ℃ of reactions 2 hours, the reactant dehydrating condensation, aquifer yield reaches about 55% of theoretical value approximately, is warming up to 150 ℃ to 210 ℃, vacuumizes reaction 2 hours, aquifer yield reaches about 98% of theory, be cooled to room temperature, discharging obtains the modification polyarylester V of the darker flowability of color not as embodiment 4.
Two, the synthetic method of grafted copolymerized emulsion
1, prescription:
The raw material consumption
Modification polyarylester 50 (gram)
Polyoxyethylene glycol (A) 30 (gram)
Vinylformic acid (AA) 0.4-1 (mole)
Acrylamide (AM) 0.4-0.8 (mole)
Deionized water 200ml
APS 2% aqueous solution is an amount of
NaHSO
32% aqueous solution is an amount of
2, embodiment 6
Accurately take by weighing modification polyarylester A 50 gram, add in the reactor, add the consumption of A in the prescription, add entry, be warming up to about 40 ℃, start stirring simultaneously, treat that content disperses when preferable logical N
2Add AA, AM, after reactant is stirred, be warming up to 45 ℃ to 50 ℃, drip initiator A PS and NaHSO
3Be warming up to 60 ℃ at a slow speed, to be triggered dose add after, stop heating, be warming up to 75 ℃ to 80 ℃ automatically, react 3 hours, the oyster white viscous fluid, be warming up to 85 ℃ of reactions 1 hour, make monomer change into graftomer fully, lower the temperature, with an amount of NaOH aqueous solution or NH
4The OH neutralization reactant, controlling its pH value is 7, discharging obtains the castor oil modified polyarylester grafted copolymerized emulsion (spinning sizing agent) of the thick flowability of scentless oyster white.
3, embodiment 7
Accurately take by weighing modification polyarylester B 50 gram, embodiment 6 is pressed in other operations, obtains the copolymer emulsion similar to embodiment 6, and flowability is slightly poorer than the product of embodiment 6.
4, embodiment 8
Accurately take by weighing modification polyarylester C 50 gram, embodiment 6 is pressed in other operations, obtains the copolymer emulsion similar to embodiment 6, good fluidity.
5, embodiment 9
Accurately take by weighing modification polyarylester D 50 gram, embodiment 9 is pressed in other operations, obtains similar copolymer emulsion flowability and is better than that embodiment 8 emulsions+but color is not so good as the emulsion of embodiment 8.
6, embodiment 10
Accurately take by weighing modification polyarylester E, other operations obtain the good fluidity similar to embodiment 6 by embodiment 6 but the color copolymer emulsion more yellow slightly than embodiment 9 emulsions.
With above-mentioned 5 kinds of representational copolymer emulsions, also can be made into the powdery granule.With the mutual solubility of native starch and other compositions of slurry and water-soluble all good, formula of size can be modulated into the very strong spinning sizing agent of suitability and use for the on-the-spot allotment of user routinely.
Claims (7)
1, a kind of making method of castor oil modified polyarylester graft copolymerization spinning sizing agent, it is characterized in that: the first step, the synthetic method of castor oil modified unsaturated polyester aromatic ester, with Viscotrol C and Tetra hydro Phthalic anhydride and MALEIC ANHYDRIDE and polyoxyethylene glycol raw material, synthesize castor oil modified polyarylester through the polymer polycondensation; Second step, the synthetic method of grafted copolymerized emulsion, the unsaturated double-bond on the above-mentioned modification polyarylester macromolecular chain is under action of evocating, carry out macromolecular grafted copolyreaction with acrylic acid or the like and acrylamide monomer, draw castor oil modified polyarylester graft copolymerization spinning sizing agent.
2, according to the making method of the described castor oil modified polyarylester graft copolymerization spinning sizing agent of claim 1, it is characterized in that: the synthetic method of described castor oil modified unsaturated polyester aromatic ester, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, Viscotrol C, polyoxyethylene glycol are dropped in the reactor, under pure N2 protection, heating, stir, the fs temperature control reacted 2 hours at 100 ℃ to 150 ℃; The subordinate phase temperature control is at 180 ℃ to 210 ℃, and the later stage suitably vacuumizes, and aquifer yield reaches about 95% of theoretical aquifer yield, obtains flaxen castor oil modified unsaturated polyester aromatic ester, cooling back discharging.
3, according to the making method of the described castor oil modified polyarylester graft copolymerization spinning sizing agent of claim 2, it is characterized in that: the synthetic method of described grafted copolymerized emulsion, quantitative water, unsaturated polyester aromatic ester, vinylformic acid, acrylamide are added in the reactor, fully stir, at pure N
2Protection drip down initiator, early stage temperature control 40 ℃ to 65 ℃ 2 hours, the later stage was warming up to 65 ℃ to 85 ℃, obtained the oyster white slurry through 2 hours, cooling back discharging.
4, according to the making method of claim 1 or 2 or 3 described castor oil modified polyarylester graft copolymerization spinning sizing agents, it is characterized in that: used graft copolymerization evocating agent is the redox initiation system that ammonium persulphate and sodium bisulfite are formed.
5, according to the making method of claim 1 or 2 described castor oil modified polyarylester graft copolymerization spinning sizing agents, it is characterized in that: the synthetic method of described castor oil modified unsaturated polyester aromatic ester, prescription is:
The raw material consumption
Polyoxyethylene glycol 1.5-2.5 mole
Tetra hydro Phthalic anhydride 1.0-2.0 mole
MALEIC ANHYDRIDE 0.5-1.0 mole
Viscotrol C 100-120 gram
The vitriol oil is a small amount of.
6, according to the making method of claim 1 or 3 described castor oil modified polyarylester graft copolymerization spinning sizing agents, it is characterized in that: the synthetic method of described grafted copolymerized emulsion, prescription is:
The raw material consumption
Modification polyarylester 50 grams
Polyoxyethylene glycol 30 grams
Vinylformic acid 0.4-1 mole
Acrylamide 0.4-0.8 mole
Deionized water 200ml
(NH
4)
2S
2O
82% aqueous solution is an amount of
NaHSO
32% aqueous solution is an amount of.
7, the castor oil modified polyarylester graft copolymerization spinning sizing agent of making according to the described method of the arbitrary claim of claim 1-6, it is characterized in that: described slurry is emulsion or powdery granule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03138724 CN1207318C (en) | 2003-06-26 | 2003-06-26 | Process for producing castor oil modified polyarylester graft copolymer textile size and size |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03138724 CN1207318C (en) | 2003-06-26 | 2003-06-26 | Process for producing castor oil modified polyarylester graft copolymer textile size and size |
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|---|---|
| CN1473860A CN1473860A (en) | 2004-02-11 |
| CN1207318C true CN1207318C (en) | 2005-06-22 |
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|---|---|---|---|
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Cited By (1)
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| CN102274371B (en) * | 2011-08-12 | 2013-04-17 | 冉好强 | Ointment for treating burn, traumatic infection and pressure sore |
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| MX352188B (en) * | 2011-03-16 | 2017-11-10 | Stepan Co | Method for producing o-phthalate polyester polyols with low cyclic ester content. |
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2003
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102274371B (en) * | 2011-08-12 | 2013-04-17 | 冉好强 | Ointment for treating burn, traumatic infection and pressure sore |
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