CN100537888C - A kind of fortifying fibre auxiliary agent and manufacture method thereof - Google Patents
A kind of fortifying fibre auxiliary agent and manufacture method thereof Download PDFInfo
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- CN100537888C CN100537888C CNB2007100571934A CN200710057193A CN100537888C CN 100537888 C CN100537888 C CN 100537888C CN B2007100571934 A CNB2007100571934 A CN B2007100571934A CN 200710057193 A CN200710057193 A CN 200710057193A CN 100537888 C CN100537888 C CN 100537888C
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Abstract
The present invention relates to a kind of fortifying fibre auxiliary agent and manufacture method thereof, the percentage by weight prescription of this auxiliary agent is: aliphatic polyoxy ethylene, propylene ether 50-70%; Double type surfactant 10-30%; Water surplus; This manufacture method adopts described auxiliary formula and following technology: prepare aliphatic polyoxy ethylene, propylene ether 1., 2. prepare the double type surfactant, 3. the percentage by weight formula rate by fortifying fibre auxiliary agent of the present invention mixes each component, fully stirred 30～90 minutes, can obtain described fortifying fibre auxiliary agent.This fortifying fibre auxiliary agent has that good fiber is uniformly dispersed, wettability, emulsibility and biological degradability, and stable performance, uses easily; This fortifying fibre manufacturing approach craft is simple, and equipment is had no special requirements, and is easy to apply.
Description
Technical field
The present invention relates to a kind of chemical fibres assistant, be specially a kind of composite fortifying fibre auxiliary agent and manufacture method thereof, international Patent classificating number intends being Int.Cl.C04B 30/00 (2006.01).
Background technology
The principal item of chemical fibre is staple fibre.The staple fibre majority is civilian or low grade products, and at present domestic supply exceed demand.The ratio of external industrial staple fibre has surpassed civilian fiber, for example, will cut into the staple fibre of 1-20mm or other length abroad, add in concrete or the pitch, make concrete or pitch fibers reinforced composite, thereby improved their performance greatly.Staple fibre in this fibre reinforced composites is commonly referred to as fortifying fibre.But fibre reinforced composites have influenced fortifying fibre performance of composites and quality and actual applying to a great extent because of the feature of fortifying fibre self makes its skewness in composite.Fortifying fibre is used for the research and development of aspects such as concrete, pitch, specialties, and is still blank at present at home.
The production technology and the conventional fibre of fortifying fibre itself are roughly the same.Fortifying fibre needs to add a kind of special assistant that puts on fiber surface as the enhancing body of composite in its production technology, so that it has good dispersiveness in the application system in downstream, unrest uniformly be can in being enhanced system (as pitch, concrete system), form to support, thereby fortifying fibre performance of composites and quality improved; Perhaps a certain proportion of fortifying fibre is incorporated in the paper pulp, obviously improves the quality uniformity of paper and increases paper strength, increases substantially the application performance of paper.This auxiliary agent is the fortifying fibre auxiliary agent.
As seen by above-mentioned, a kind of special use or special auxiliary agent is a key technology of making the fortifying fibre that can satisfy the extensive needs in downstream.In the scope of applicant's literature search, be applicable to the fortifying fibre auxiliary agent of above all kinds of composite or purposes, have not yet to see report.
Summary of the invention
At the deficiency of above-mentioned technology, the technical problem to be solved in the present invention is to design a kind of fortifying fibre auxiliary agent and manufacture method thereof.This fortifying fibre auxiliary agent has that good fiber is uniformly dispersed, wettability, emulsibility and biological degradability, and stable performance, uses easily; This fortifying fibre manufacturing approach craft is simple, and equipment is had no special requirements, and is easy to apply.
The technical scheme that the present invention solves described auxiliary agent technical problem is, designs a kind of fortifying fibre auxiliary agent, and its percentage by weight is formed and comprised:
Aliphatic polyoxy ethylene, propylene ether 50-70%;
Double type surfactant 10-30%;
Water surplus,
Described aliphatic polyoxy ethylene, propylene ether is made by following method: the saturated fatty alcohol that adds 0.25-0.5 mole of C8-C16 saturated fatty acid or C8-C16 in autoclave is an initiator, vacuumize, nitrogen replacement 4 times, with the potassium hydroxide that accounts for reaction-ure mixture 1-5wt ‰ is catalyst, be warming up to 120-130 ℃, to under negative pressure, mix molal quantity and be 10-50 polyoxyethylene and molal quantity and be 10-40 polyoxypropylene and feed reactor, reaction pressure is controlled under 0.3-0.4Mpa, carry out oxirane, the expoxy propane ring-opening reaction no longer changes until reaction pressure; Be cooled to 70-99 ℃, emptying, discharging promptly get target product;
Described double type surfactant is C
8-C
12Saturated straight chain or the oligomeric diol that generates of the glycidol ether of branched fatty alcohol and glycol reaction, the double type phosphate ester salt that obtains through phosphorylation again; Concrete grammar is: add 0.25-1.0 moles of ethylene glycol, 2.0Kg metallic potassium catalyst and 0.1-0.4 mole of C in reactor
8-C
12Saturated straight chain or the glycidol ether of branched fatty alcohol, be warming up to 70-80 ℃, reaction 8h will react the filtration of resulting mixed liquor, the elimination solid can make the intermediate oligomeric diol; The gained intermediate is carried out decompression distillation purify the oligomeric diol that obtains making with extra care; Refining oligomeric diol and phosphorus pentoxide are added reactor according to the mol ratio of 2.5:1 carry out phosphorylation reaction, stir, be warming up to 75-85 ℃, reaction 6-10h obtains rough solid phosphate ester; Again solid phosphate ester is heated to fusing, adds distilled water and potassium hydroxide solid particle while stirring successively, 40-60 ℃ of following insulated and stirred 1-2h, discharging promptly gets target product.
The technical scheme that the present invention solves described manufacture method technical problem is, designs a kind of manufacture method of fortifying fibre auxiliary agent, and this manufacture method adopts following technology:
(1) preparation aliphatic polyoxy ethylene, propylene ether:
In autoclave, add 0.25～0.5 mole of C
8～C
16Saturated fatty acid or C
8～C
16Saturated fatty alcohol be initiator, vacuumize, nitrogen replacement 4 times, with the potassium hydroxide that accounts for reaction-ure mixture 1～5wt ‰ is catalyst, be warming up to 120～130 ℃, will mix molal quantity and be 10～50 polyoxyethylene and molal quantity under negative pressure and be 10～40 polyoxypropylene and feed reactor, reaction pressure is controlled under 0.3～0.4Mpa, carry out oxirane, expoxy propane ring-opening reaction, no longer change until reaction pressure; Be cooled to 70～99 ℃, emptying, discharging promptly get target product;
(2) preparation double type surfactant:
In reactor, add 0.25～1.0 mole of ethylene glycol, 2.0Kg metallic potassium catalyst and 0.1～0.4 mole of C
8-C
12Saturated straight chain or the glycidol ether of branched fatty alcohol, be warming up to 70～80 ℃, reaction 8h will react the filtration of resulting mixed liquor, the elimination solid can make the intermediate oligomeric diol; The gained intermediate is carried out decompression distillation purify the oligomeric diol that obtains making with extra care; Refining oligomeric diol and phosphorus pentoxide are added reactor according to the mol ratio of 2.5:1 carry out phosphorylation reaction, stir, be warming up to 75～85 ℃, reaction 6～10h obtains rough solid phosphate ester; Again solid phosphate ester is heated to fusing, adds distilled water while stirring successively, the potassium hydroxide solid particle, 40～60 ℃ of following insulated and stirred 1～2h, discharging promptly gets target product;
(3) formulation aid:
Percentage by weight proportion of composing by fortifying fibre auxiliary agent of the present invention mixes each component, fully stirs 30～90 minutes, can obtain described fortifying fibre auxiliary agent.
Compared with prior art, fortifying fibre auxiliary agent of the present invention is the auxiliary formula of main component because designed with aliphatic polyoxy ethylene, propylene ether and double type surfactant, thereby have and to give that it is enough uniformly dispersed in the fibre reinforced materials system, make fortifying fibre in being enhanced system, form a kind of uniform unrest to support system, improve the performance or the function of the system that is enhanced effectively, and stable performance, easy-to-use characteristics.Fortifying fibre manufacture method key of the present invention is synthetic described aliphatic polyoxy ethylene, propylene ether and double type surfactant, and complex process is very simple, and equipment is had no special requirements, and is easy to apply.
Description of drawings
Fig. 1 is the process flow diagram of fortifying fibre auxiliary agent manufacture method of the present invention.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment, but the present invention is not subjected to the restriction of embodiment.
A kind of fortifying fibre auxiliary agent of the present invention (hereinafter to be referred as auxiliary agent), its percentage by weight is formed and is comprised:
Aliphatic polyoxy ethylene, propylene ether 50～70%;
Double type surfactant 10～30%;
Water surplus.
The structural formula of the aliphatic polyoxy ethylene, propylene ether in the auxiliary formula of the present invention is: RO-(CH
2CH
2O) n
2-(CH
2CHCH
3O) m
2H, alkyl chain wherein are C
8-C
16Saturated fatty acid or C
8-C
16Saturated fatty alcohol, polyoxyethylene segment (EO) molal quantity are 10-50, polyoxypropylene segment (PO) molal quantity is 10-40, polyoxyethylene ether and polyoxypropylene segment are random form, and molecular weight is more than or equal to 4000.Described aliphatic polyoxy ethylene, propylene ether is a kind of new non-ionic surface active agent that the present invention designs, is to have the new structure polyether monomer, and for the polymeric main smooth agent in the prescription, be one of key technology of auxiliary agent of the present invention.It has the lubricating film that can form solid state at fiber surface, prevents to form adhesion in the process of fiber dispersion in the enhancing system; After fiber entered in the water, this layer lubricating film still can keep the dry and comfortable state of fiber surface, can effectively prevent coalescent and sticking the twining of fiber, helps the even dispersion of fiber simultaneously.Conventional non-ionic surface active agent molecular weight major part concentrates on about 500-1000, and majority be liquid state at normal temperatures, is not easy attached to fiber surface; Be solid-state though have under the non-ionic surface active agent normal temperature of small part routine, meet behind the water, cause its apparent viscosity to increase, be unfavorable for very much the dispersion of fiber because the part of its molecule is melted.Aliphatic polyoxy ethylene, propylene ether molecular weight of the present invention is different from prior art fully more than or equal to 4000.
Double type surfactant in the auxiliary formula of the present invention is C
8-C
12Saturated straight chain or the oligomeric diol that generates of the glycidol ether of branched fatty alcohol and glycol reaction, the double type phosphate ester salt that obtains through phosphorylation again; Its structural formula is:
Described double type surfactant double type phosphate also is a kind of novel surfactant monomer that the present invention designs, and also is one of key technology of auxiliary agent of the present invention.Contain two ionization hydrophilic groups in the double type phosphate ester surfactants molecular structure, can combine better, and have antistatic behaviour preferably with hydrone; Its hygroscopicity is much smaller than the conventional phosphate ester salt contrast product with same carbon chain length simultaneously.Double type surfactant double type phosphate of the present invention is used for textile auxiliary, and the adherence of auxiliary agent is descended greatly; There are two hydrophobic chains because it has again, thereby have good wettability, emulsibility and biological degradability, and multiple characteristics such as foam is few.Double type phosphate of the present invention is also referred to as the caking inhibiter at multi-charge center, can effectively prevent gathering, sticking twining that staple fibre causes because of electrostatic attraction or apparent adhesion in the enhancing system, and staple fibre is uniformly dispersed.
Prescription of the present invention is further characterized in that and also comprises 5-10% alkylol phosphate kalium salt or alkyl alcohol ether phosphate kalium salt or their phosphate amine salt in the described auxiliary agent percentage by weight prescription.The purpose that adds phosphate ester salt in the described prescription is the antistatic effect of further reinforcing aids, improves the adaptability of prescription.The conventional products that described phosphate kalium salt, alkyl alcohol ether phosphate kalium salt or their amine salt (EO=3 or 10) are produced for the applicant.
In order to improve the stability of auxiliary agent, prescription of the present invention is further characterized in that in the described auxiliary agent percentage by weight prescription and also comprises 10-30% emulsifying agent.Described emulsifying agent is any one among commercially available peregal, O-9 or the OP-10 etc.Described emulsifying agent all keeps its stability in the time of can guaranteeing the stoste of auxiliary agent product and aqueous solution state, even auxiliary agent is not stratified when former liquid status is deposited, is uniformly dispersed in the aqueous solution when using with aqueous solution state.
In order to improve the wettability of auxiliary agent, the further feature of prescription of the present invention also is to comprise 3-5% bleeding agent in the described percentage by weight prescription.Described bleeding agent is any one among commercially available JFC, PF-C, KD-TD41 etc.Described bleeding agent can permeate with wetting the fiber that will disperse effectively, guarantees auxiliary agent cladding uniformity on fiber, helps the raising of additive performance.
Water in the described prescription is distilled water or deionized water.Adding it is for each component that makes auxiliary agent evenly spreads, and increases the stability of adjuvant system.
Phosphate kalium salt of the present invention, emulsifying agent and bleeding agent are market and easily purchase and be easy to get conventional products with low cost.In described prescription, add phosphate kalium salt, emulsifying agent or/and behind the bleeding agent, the solvent ratio of prescription can suitably be adjusted, to satisfy the requirement of prescription 100% in former scope.
The design principle and the function of auxiliary agent of the present invention are:
1. improve the wettability of fiber surface
Most synthetic fiber are hydrophobic fibre.Fiber enters and often is pencil in the water, and is surrounded by air.The fiber that enters in the water is scatter fully and the air that it is surperficial replaces out, needs a motive force S:
S＝γsg-(γsl+γlg)，
In the formula: S: adhesion work refers to separate the needed merit of unit are between the two-phase; γ sg: solid phase/gas phase interface tension force; γ sl: solid phase/liquid interface tension force; γ lg: liquid/solid phases interfacial tension.
As S〉0 the time, contact angle is zero, liquid is spontaneous to be sprawled on the fiber grain surface.SURFACTANT ADSORPTION in water and fiber interface chien shih γ sl and γ lg decline, thereby makes S behind fiber surface〉0, water can be carried out smoothly sprawling of fiber surface.In addition, surfactant is owing to have the amphiphile, amphiphilic molecule of hydrophilic and oleophilic, be adsorbed on hydrophobic fiber surface after, its hydrophobic group near fiber surface and hydrophilic group outwardly, help improving the wettability of water, thereby improve the wettability of fiber in water fiber surface.
2. improve the dispersiveness of fiber
Undressed fiber itself is electroneutral.The caking inhibiter at the multi-charge center of the present invention's design adopts the surfactant with a plurality of ionic groups, orientable absorption is arranged in fiber surface, fiber surface is surrounded by the Ionized surfactant of one deck, thereby hinder or prevented the coalescent mutually of fiber, make it to keep the good homogeneous dispersity.In addition, after fiber entered in the water, its hydrophobic wax shape surface had huge surface area, and surface energy is very big, is thermodynamic unstable system.When the SURFACTANT ADSORPTION of the present invention design behind fiber surface, γ sl is reduced, thereby can greatly reduce its surface free energy, reduce fiber coalescent trend mutually, also help improving the uniformly dispersed of fiber.
3. the rigidity of reinforcing fibre
The general staple fibre that requires to be cut to 1-20mm of fortifying fibre.This length is significantly smaller than routine and takes staple fibre and (be generally 38～102mm) length, therefore to the cut-out demands for higher performance of fortifying fibre.Soft without the fiber that auxiliary agent is handled, rigidity is lower, and in the cutting-off process of fiber, occur the phenomenon of overlength, double-length easily, thereby cause fibre length to differ, and then dispersed inhomogeneous in water, and winding mutually easily.The present invention adds an amount of macromolecule smooth agent aliphatic polyoxy ethylene, propylene ether in the prescription of auxiliary agent, make it to form solid lubricant film at fiber surface, can increase the apparent rigidity of fiber, reduces the bonding between the fiber simultaneously.
Fortifying fibre auxiliary agent manufacture method of the present invention (abbreviation manufacture method) adopts the percentage by weight prescription and the following processing step (referring to Fig. 1) of fortifying fibre auxiliary agent of the present invention:
This manufacture method adopts following technology:
1. prepare aliphatic polyoxy ethylene, propylene ether:
The C that in autoclave, adds 0.25～1.0 mole
8-C
16Saturated fatty acid or C
8-C
16Saturated fatty alcohol be initiator, vacuumize, nitrogen replacement 4 times, with the potassium hydroxide that accounts for reaction-ure mixture 1～5wt ‰ is catalyst, be warming up to 120～130 ℃, polyoxyethylene that will mix under negative pressure (molal quantity is 10～50) and polyoxypropylene (molal quantity is 10～40) feed reactor, and reaction pressure is under 0.3～0.4Mpa, carry out oxirane, expoxy propane ring-opening reaction, no longer change until reaction pressure; Be cooled to 70～99 ℃ of emptying, discharging promptly gets target product;
2. prepare the double type surfactant:
Add 0.25～1.0 mole of ethylene glycol in reactor, the metallic potassium catalyst of 1～5wt ‰ and 0.1～0.4 mole of positive alkyl glycidyl ether are warming up to 70～80 ℃, reaction 8h, to react resulting mixed liquor and filter, the elimination solid can make the intermediate oligomeric diol; The gained intermediate is carried out decompression distillation purify the oligomeric diol that obtains making with extra care; Refining oligomeric diol and phosphorus pentoxide are added reactor according to the mol ratio of 2.5:1 carry out phosphorylation reaction, stir, be warming up to 75～85 ℃, reaction 6～10h obtains rough solid phosphate ester; Again solid phosphate ester is heated to fusing, adds distilled water while stirring successively, the potassium hydroxide solid particle, 40～60 ℃ of following insulated and stirred 1～2h, discharging can get target product;
3. formulation aid:
Percentage by weight formula rate by fortifying fibre auxiliary agent of the present invention mixes each component, fully stirs 30-90 minute, can obtain described fortifying fibre auxiliary agent.
The manufacture method of auxiliary agent of the present invention, its feature also is in the described macromolecule smooth agent manufacture process after the emptying, also comprise following technology: the phosphoric acid that adds 0.3-0.5 ‰ earlier, regulate the pH value to 7-8 of product, stir after 30 minutes, add the adsorbent magnesium silicate of 0.1-3% again, continue insulation and stirring 40-70 minute, cocrystallization is handled the back and is filtered, and behind the metal ion in the removal product, can obtain described target product.
Manufacture method of the present invention in the manufacture process of described macromolecule smooth agent, the catalyst KOH that has used.What it helped reacting carries out fast.But base catalyst needs to neutralize when reaction finishes.Common production method is to adopt the acetic acid neutralization.But the salt that the neutralization back generates can not form crystallization, thereby can't remove, but remains in the polymer particle product, can not satisfy the requirement of fiber dispersion; In order to solve this technical problem, in the building-up process of auxiliary agent aliphatic polyoxy ethylene, propylene ether of the present invention, designed the new method of phosphoric acid neutralization, blend crystallization and adding adsorbent.It and common neutralization method are not both: after being cooled to uniform temperature, emptying is selected for use in the phosphoric acid and metal K
+Ion, thus removable crystal salt grain can and be formed easily; After adding the adsorbent synthetic magnesium silicate, can make not the metal K of neutralization fully
+Ion and short grained crystallization are adsorbed by the adsorbent that is added synthetic magnesium silicate; Again by filtering, described crystal salt grain and adsorbent can be removed simultaneously, institute's metal remained ion in removing effectively and in the technology is controlled at the content of metal ion below the 20ppm, has solved polymer particle metal ion content height, the bad problem of fiber dispersion.Described catalyst is a metal base, as potassium hydroxide etc.; Described adsorbent is a synthetic magnesium silicate.But this does not also mean that the identical chemical substance of other character cannot use.
The performance indications of fortifying fibre auxiliary agent product of the present invention are as described in Table 1:
(table 1)
| Project | TFS-90 |
| Outward appearance | The sundown paste |
| Solid content (%) | 80±2 |
| PH value (1%) | 7±1 |
| Stability of emulsion | 10% additive latex, 48 hours stable |
| Surface tension | 28±3mN/cm |
| Wetting power | <10sec |
| After using this product, fiber dispersion power | 0-1 grade (company standard) |
Auxiliary agent of the present invention belongs to textile auxiliary, does not have relevant national standard or industry standard at present.Listed each quality index of table 1 and assay method thereof are all carried out with reference to existing petrochemicals GB.Wherein the mensuration of dispersion force is carried out company standard, and standard No. is: QT 0542-2005.Its particular content is as follows:
Get the fiber (5-6mm) that 0.4g cuts off, pour in the 1000ml large beaker that fills 900g water, stirred 1 minute, be ferreted out with screen cloth then, in baking oven, dry, take the fibre sheet of screen surface then off; Fibre sheet is attached on the black paper (or red paper), observes the uniformity of fibre sheet, then by following standard grading:
0 grade: copy the fiber that does not have bonding on the paper fibre sheet;
1 grade: copying has 1-2 group fiber to be bonded together on the paper fibre sheet, all the other are single dispersity;
2 grades: copying has 3-5 group fiber to be bonded together on the paper fibre sheet, all the other are single dispersity;
3 grades: copying has 6-10 group fiber to be bonded together on the paper fibre sheet, all the other are single dispersity;
4 grades: copying has the fiber greater than 10 groups to be bonded together on the paper fibre sheet, all the other are single dispersity;
5 grades: copying has a large amount of fibers to be bonded together on the paper fibre sheet.
Auxiliary agent of the present invention is applicable to the in extensive range of fortifying fibre, comprises the fortifying fibre of various routines such as terylene, acrylic fibers, polypropylene fibre, polyamide fibre.
Auxiliary agent of the present invention is applicable to needs fortifying fibre evenly to disperse in composite system, and gram forms disorderly in the product manufacture of support system, for example can be applicable in fibre reinforced cement system, the fibre reinforced asphalt system, can improve the ability of the cracking resistance of concrete, asphalt system, impervious, shock resistance and anti-settling, prolong the ageing time of composite; For example can be applicable to again in the manufacturing technique of functional paper or speciality paper,, increase substantially the application performance of paper with quality uniformity and the increase strength of paper of improving paper effectively; For example can be applicable to again in the electrostatic spinning manufacturing process and product, solve sticking cutter, the flyings of electrostatic spinning process, problem such as fiber dispersion is irregular, and static is big.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below, but the present invention is not subjected to the restriction of embodiment.
Embodiment 1:
In autoclave, add initiator dodecoic acid 50kg, and catalyst (KOH) 2.0kg, vacuumize, again through nitrogen replacement 4 times, be warming up to 120 ℃, under negative pressure, feed the 880kgEO (the EO molal quantity is 20) that mixes, 580kgPO (the PO molal quantity is 10) keeps reaction pressure under 0.3-0.4Mpa, continues reaction and is not changing emptying until pressure, be cooled to 80 ℃, add phosphatase 24 .0kg and stir 30min, add adsorbent synthetic magnesium silicate 1.0kg, continue to stir 60 minutes, filter, can obtain product A
1
In reactor, add 100kg ethylene glycol, add 2.5kg metallic potassium (catalyst) again, start agitator simultaneously.After metallic potassium dissolves fully in the question response liquid 600kg octanol glycidol ether is added in the reaction system, then with more than the reactant liquor heat temperature raising to 60 ℃, reaction 10～20h.With the reactant mixture decompression distillation, remove unreacted ethylene glycol after having reacted, the intermediate that obtains making with extra care is thrown phosphorus at substep below 60 ℃, finishes the phosphorylation of intermediate, and neutralization, filtration obtain B component
1
In 1 ton stainless steel still, add product A
1250kg is heated to 50 ℃, adds product B
1100kg, water 13kg maintains the temperature at 50 ℃, continues to stir 1 hour, obtains described auxiliary agent Z
1The dispersion force of fiber reaches 3 grades after testing.
Embodiment 2:
In autoclave, add initiator lauryl alcohol 50kg, and catalyst (KOH) 2.0kg, vacuumize, again through nitrogen replacement 4 times, be warming up to 120 ℃, under negative pressure, feed the 880kgEO (the EO molal quantity is 20) that mixes, 580kgPO (the PO molal quantity is 10) keeps reaction pressure under 0.3-0.4Mpa, continues reaction and is not changing emptying until pressure, be cooled to 80 ℃, add phosphatase 24 .0kg and stir 30min, add adsorbent synthetic magnesium silicate 1.0kg, continue to stir 60 minutes, filter, can obtain product A
2
In reactor, add 100kg ethylene glycol, add 2.5kg metallic potassium (catalyst) again, start agitator simultaneously.After the metallic potassium complete obiteration 600kg laruyl alcohol glycidol ether is added in the reaction system in the question response liquid, then with more than the reactant liquor heat temperature raising to 60 ℃, reaction 10～20h.With the reactant mixture decompression distillation, remove unreacted ethylene glycol after having reacted, the intermediate that obtains making with extra care is thrown phosphorus at substep below 60 ℃, finishes the phosphorylation of intermediate, and neutralization, filtration obtain B component
2
In 1 ton stainless steel still, add product A
1250kg is heated to 50 ℃, adds product B
2100kg adds C
2Laruyl alcohol phosphate kalium salt 50kg, water 8.5kg maintains the temperature at 50 ℃, continues to stir 1 hour, obtains auxiliary agent Z
2The dispersion force of fiber reaches 2 grades after testing.
Embodiment 3:
In autoclave, add initiator palmitic acid 100kg, and catalyst (KOH) 2.0kg, vacuumize, again through nitrogen replacement 4 times, be warming up to 120 ℃, under negative pressure, feed the 1320kgEO (molal quantity of EO is 30) that mixes, 580kgPO (molal quantity of PO is 10) keeps reaction pressure under 0.3-0.4Mpa, continues reaction and is not changing emptying until pressure, be cooled to 80 ℃, add phosphatase 24 .0kg and stir 30min, add adsorbent synthetic magnesium silicate 1.0kg, continue to stir 60 minutes, filter, can obtain product A
3
In reactor, add 100kg ethylene glycol, add 2.5kg metallic potassium (catalyst) again, start agitator simultaneously.After the metallic potassium complete obiteration 600kg octanol glycidol ether is added in the reaction system in the question response liquid, then with more than the reactant liquor heat temperature raising to 60 ℃, reaction 10～20h.With the reactant mixture decompression distillation, remove unreacted ethylene glycol after having reacted, the intermediate that obtains making with extra care is thrown phosphorus at substep below 60 ℃, finishes the phosphorylation of intermediate, and neutralization, filtration obtain B component
3
In 1 ton stainless steel still, add product A
1250kg is heated to 50 ℃, adds product B
1100kg adds 12-14 pure phosphate kalium salt 50kg, adds D1 Emulsifier O-925kg, and water 6kg maintains the temperature at 50 ℃, continues to stir 1 hour, obtains auxiliary agent Z
3The dispersion force of fiber reaches 1 grade after testing.
Embodiment 4:
In autoclave, add initiator laurate 50kg, and catalyst (KOH) 2.0kg, vacuumize, again through nitrogen replacement 4 times, be warming up to 120 ℃, under negative pressure, feed the 110kgEO (molal quantity of EO is 25) that mixes, 1160kgPO (molal quantity of PO is 20) keeps reaction pressure under 0.3-0.4Mpa, continues reaction and is not changing emptying until pressure, be cooled to 80 ℃, add phosphatase 24 .0kg and stir 30min, add adsorbent synthetic magnesium silicate 1.0kg, continue to stir 60 minutes, filter, can obtain product A
4
In reactor, add 100kg ethylene glycol, add 2.5kg metallic potassium (catalyst) again, start agitator simultaneously.After the metallic potassium complete obiteration 500kg laruyl alcohol glycidol ether is added in the reaction system in the question response liquid, then with more than the reactant liquor heat temperature raising to 60 ℃, reaction 10～20h.With the reactant mixture decompression distillation, remove unreacted ethylene glycol after having reacted, the intermediate that obtains making with extra care is thrown phosphorus at substep below 60 ℃, finishes the phosphorylation of intermediate, and neutralization, filtration obtain B component
4
In 1 ton stainless steel still, add product A
4250kg is heated to 50 ℃, adds product B
4100kg adds C
4Laruyl alcohol phosphate kalium salt 50kg adds D
4Emulsifier O-925kg, E
4Penetrating agent JFC 75kg,
Water 12kg maintains the temperature at 50 ℃, continues to stir 1 hour, obtains auxiliary agent Z
4The dispersion force of fiber reaches 0 grade after testing.
Embodiment 5:
In autoclave, add initiator lauryl alcohol 100kg, and catalyst (KOH) 4kg, vacuumize, again through nitrogen replacement 3-4 time, be warming up to about 110 ℃, feed 1420kgEO (molal quantity of EO is 30) under negative pressure, 1500kgEO (molal quantity of PO is 26) keeps reaction pressure under 0.3-0.4Mpa, continuing reaction is not changing until pressure, emptying is cooled to 90 ℃, adds phosphoric acid 2.05kg and stirs 30min, add synthetic magnesium silicate 0.3kg, continue to stir 60 minutes, filter, can obtain product A
2
In reactor, add 100kg ethylene glycol, add 3.0kg metallic potassium (catalyst) again, start agitator simultaneously.After the metallic potassium complete obiteration 700kg laruyl alcohol glycidol ether is added in the reaction system in the question response liquid, then with more than the reactant liquor heat temperature raising to 60 ℃, reaction 15h.With the reactant mixture decompression distillation, remove unreacted ethylene glycol after having reacted, the intermediate that obtains making with extra care is thrown phosphorus at substep below 60 ℃, finishes the phosphorylation of intermediate, and neutralization, filtration obtain B component
5
In 1 ton stainless steel still, add product A
5175kg is heated to 50 ℃, adds product B
525kg adds C
5Lauryl alcohol phosphate amine salt (EO=3) 12.5kg adds penetrating agent JFC 10kg, adds 27.5kg water, maintains the temperature at 30 ℃, continues to stir 1 hour, obtains auxiliary agent Z
5The dispersion force of fiber reaches 1 grade after testing.
Embodiment 6:
In autoclave, add initiator octanol 40kg, and catalyst (KOH) 1.75kg, vacuumize, again through nitrogen replacement 3-4 time, be warming up to about 100 ℃, under negative pressure, feed 660kgEO (several moles of EO is 15), 1160kgEO (molal quantity of PO is 20), keep reaction pressure under 0.3-0.4Mpa, continue reaction and do not changing until pressure, emptying is cooled to 80 ℃, add phosphoric acid 3.6kg, stir 30min, add synthetic magnesium silicate 0.6kg, continue to stir 60 minutes, filter, can obtain product A
6
In reactor, add 100kg ethylene glycol, add 2.5kg metallic potassium (catalyst) again, start agitator simultaneously.In the question response liquid after the metallic potassium complete obiteration with 700kgC
8-10The alcohol glycidol ether adds in the reaction system, then with more than the reactant liquor heat temperature raising to 65 ℃, and reaction 16h.With the reactant mixture decompression distillation, remove unreacted ethylene glycol after having reacted, the intermediate that obtains making with extra care is thrown phosphorus at substep below 60 ℃, finishes the phosphorylation of intermediate, and neutralization, filtration obtain B component
6
In 1 ton stainless steel still, add product A
6400kg is heated to 50 ℃, adds product B
660kg adds C
6Octanol ether (EO=10) phosphate amine salt 40kg adds penetrating agent JFC 20kg, adds 55kg water, maintains the temperature at 30 ℃, continues to stir 1 hour, obtains auxiliary agent Z
6The dispersion force of fiber reaches 1 grade after testing.
Claims (6)
1. fortifying fibre auxiliary agent, its percentage by weight is formed and is comprised:
Aliphatic polyoxy ethylene, propylene ether 50-70%;
Double type surfactant 10-30%;
Water surplus,
Described aliphatic polyoxy ethylene, propylene ether is made by following method: add 0.25-0.5 mole of C in autoclave
8-C
16Saturated fatty acid or C
8-C
16Saturated fatty alcohol be initiator, vacuumize, nitrogen replacement 4 times, with the potassium hydroxide that accounts for reaction-ure mixture 1-5wt ‰ is catalyst, be warming up to 120-130 ℃, will mix molal quantity and be 10-50 polyoxyethylene and molal quantity under negative pressure and be 10-40 polyoxypropylene and feed reactor, reaction pressure is controlled under 0.3-0.4Mpa, carry out oxirane, expoxy propane ring-opening reaction, no longer change until reaction pressure; Be cooled to 70-99 ℃, emptying, discharging promptly get target product;
Described double type surfactant is C
8-C
12Saturated straight chain or the oligomeric diol that generates of the glycidol ether of branched fatty alcohol and glycol reaction, the double type phosphate ester salt that obtains through phosphorylation again; Concrete grammar is: add 0.25-1.0 moles of ethylene glycol, 2.0Kg metallic potassium catalyst and 0.1-0.4 mole of C in reactor
8-C
12Saturated straight chain or the glycidol ether of branched fatty alcohol, be warming up to 70-80 ℃, reaction 8h will react the filtration of resulting mixed liquor, the elimination solid can make the intermediate oligomeric diol; The gained intermediate is carried out decompression distillation purify the oligomeric diol that obtains making with extra care; Refining oligomeric diol and phosphorus pentoxide are added reactor according to 2.5: 1 mol ratio carry out phosphorylation reaction, stir, be warming up to 75-85 ℃, reaction 6-10h obtains rough solid phosphate ester; Again solid phosphate ester is heated to fusing, adds distilled water and potassium hydroxide solid particle while stirring successively, 40-60 ℃ of following insulated and stirred 1-2h, discharging promptly gets target product.
2. fortifying fibre auxiliary agent according to claim 1 is characterized in that described percentage by weight also comprises phosphate kalium salt 5-10% in forming.
3. fortifying fibre auxiliary agent according to claim 1 is characterized in that described percentage by weight also comprises emulsifying agent 10-30% in forming.
4. fortifying fibre auxiliary agent according to claim 1 is characterized in that described percentage by weight also comprises bleeding agent 3-5% in forming.
5. the manufacture method of each described fortifying fibre auxiliary agent of claim 1-4, this manufacture method adopts following technology:
(1) preparation aliphatic polyoxy ethylene, propylene ether:
In autoclave, add 0.25-0.5 mole of C
8-C
16Saturated fatty acid or C
8-C
16Saturated fatty alcohol be initiator, vacuumize, nitrogen replacement 4 times, with the potassium hydroxide that accounts for reaction-ure mixture 1-5wt ‰ is catalyst, be warming up to 120-130 ℃, will mix molal quantity and be 10-50 polyoxyethylene and molal quantity under negative pressure and be 10-40 polyoxypropylene and feed reactor, reaction pressure is controlled under 0.3-0.4Mpa, carry out oxirane, expoxy propane ring-opening reaction, no longer change until reaction pressure; Be cooled to 70-99 ℃, emptying, discharging promptly get target product;
(2) preparation double type surfactant:
In reactor, add 0.25-1.0 moles of ethylene glycol, 2.0Kg metallic potassium catalyst and 0.1-0.4 mole of C
8-C
12Saturated straight chain or the glycidol ether of branched fatty alcohol, be warming up to 70-80 ℃, reaction 8h will react the filtration of resulting mixed liquor, the elimination solid can make the intermediate oligomeric diol; The gained intermediate is carried out decompression distillation purify the oligomeric diol that obtains making with extra care; Refining oligomeric diol and phosphorus pentoxide are added reactor according to 2.5: 1 mol ratio carry out phosphorylation reaction, stir, be warming up to 75-85 ℃, reaction 6-10h obtains rough solid phosphate ester; Again solid phosphate ester is heated to fusing, adds distilled water and potassium hydroxide solid particle while stirring successively, 40-60 ℃ of following insulated and stirred 1-2h, discharging promptly gets target product;
(3) formulation aid:
Percentage by weight proportion of composing by fortifying fibre auxiliary agent of the present invention mixes each component, fully stirs 30-90 minutes, promptly obtains described fortifying fibre auxiliary agent.
6. according to the manufacture method of the described fortifying fibre auxiliary agent of claim 5, after it is characterized in that the emptying in the described preparation aliphatic polyoxy ethylene, propylene ether process, also comprise following technology: the phosphoric acid that adds 0.3-0.5 ‰, regulate the pH value to 7-8 of product, stir after 30 minutes, add the adsorbent magnesium silicate of 0.1-3% again, continue insulation and stirring 40-70 minute, cocrystallization is handled the back and is filtered, and behind the metal ion in the removal product, promptly obtains described target auxiliary agent.
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| CN102485771A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Fatty alcohol polyoxypropylene polyoxyethylene ether carboxylate, preparation thereof and application thereof |
| CN102503821B (en) * | 2011-11-22 | 2014-04-02 | 江苏利田科技股份有限公司 | Clean production method of alkoxylation glycerol triacrylate |
| CN102491896B (en) * | 2011-11-22 | 2014-03-12 | 江苏利田科技股份有限公司 | Clean production method of dipropylene glycol diacrylate (DPGDA) or tripropylene glycol diacrylate (TPGDA) |
| CN102633635B (en) * | 2012-03-31 | 2014-02-19 | 江苏利田科技股份有限公司 | Clean production method of dipentaerythritol hexaacrylate |
| CN102633633B (en) * | 2012-03-31 | 2014-05-14 | 江苏利田科技股份有限公司 | Pollution-free production method of lauryl alcohol acrylate, hexadecanol acrylate or stearyl alcohol acrylate |
| CN102633634B (en) * | 2012-03-31 | 2014-05-14 | 江苏利田科技股份有限公司 | Cleaning production method of 2-(Ethoxyethoxy) ethyl acrylate (EOEOEA) or phenoxyethyl acrylate (PHEA) |
| CN102643197B (en) * | 2012-03-31 | 2014-07-30 | 江苏利田科技股份有限公司 | Cleaning production method for di-trimethylolpropane tetra-acrylic ester or pentaerythritol tetra-acrylic ester |
| CN103741465B (en) * | 2013-12-11 | 2016-06-22 | 江阴市尼美达助剂有限公司 | The preparation method of antistatic additive |
| CN106914584B (en) * | 2017-04-18 | 2018-10-19 | 上海金兆节能科技有限公司 | A kind of aluminium alloy casting crystallizer mould oil and preparation method thereof |
| CN108314844B (en) * | 2018-05-09 | 2020-10-30 | 常州大学 | Preparation method of modified zinc borate whisker reinforced flame-retardant waterproof breathable film |
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