CN109719925A - Terylene fire retardant canvas and preparation method thereof - Google Patents

Terylene fire retardant canvas and preparation method thereof Download PDF

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Publication number
CN109719925A
CN109719925A CN201811614100.8A CN201811614100A CN109719925A CN 109719925 A CN109719925 A CN 109719925A CN 201811614100 A CN201811614100 A CN 201811614100A CN 109719925 A CN109719925 A CN 109719925A
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fire retardant
reaction
trimethylsilyl
preparation
temperature
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CN109719925B (en
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杨超明
王山水
汤方明
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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Abstract

The present invention relates to a kind of terylene fire retardant canvas and preparation method thereof, the preparation method comprises the following steps: terylene fire retardant canvas is made in the surface calender lamination PVC film of modified polyester industrial yarns woven cloths；Modified polyester industrial yarns are by the way that modified poly ester melt is carried out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oils, stretch, made from thermal finalization, heat treatment without tension and winding；Modified poly ester the preparation method comprises the following steps: terephthalic acid (TPA), ethylene glycol, the dihydric alcohol with trimethylsilyl side group and 2- carboxyethyl phenyl hypophosphorous acid successively to be carried out to esterification and polycondensation reaction after mixing before solid phase polycondensation viscosifies；Heat treatment without tension refers to the space by modified poly ester tow in the state that the over feed rate(OFR) of winding is 3.0~5.0% by 200~240 DEG C.The good mechanical performance of product is made in preparation method of the invention, simple process and low cost, and adhesive strength is 50~60N/cm, peel strength >=8.5N/cm.

Description

Terylene fire retardant canvas and preparation method thereof
Technical field
The invention belongs to modified polyester fiber technical field, it is related to a kind of terylene fire retardant canvas and preparation method thereof.
Background technique
Ethylene glycol terephthalate (PET) fiber since the advent of the world obtains swift and violent because of the excellent performance that it has Ground development, yield have become the hat of world's synthetic fibers.Due to polyester fiber have breaking strength is high, elasticity modulus is high, Resilience is moderate, thermal finalization is had excellent performance, heat-resisting light resistance is good and a series of Optimality such as acid-fast alkali-proof good corrosion resistance Can, and fabric prepared therefrom has many advantages, such as that crease-resistant and stiffness is good, is widely used in numerous areas.In China's handle Polyethylene terephthalate content is more than that 85% polyester is known as terylene.Polyester filament is due to excellent performance, As one of highest product of yield with fastest developing speed in synthetic fibers, have in decoration, industry and textile and garment enterprise extensively Application.
With the development and progress of society, the industries such as steel, mining and cement flourish, and in these industries to conveying The demand of band is huge, especially the demand to fire-retardant transmission belt.Current fire retarding conveying band is mostly with ordinary polyester silk or nylon yarn As canvas skeleton, by improving the flame retardant property of canvas in the rubberizing of canvas surface, but rubberizing can not be impregnated with canvas completely Layer, since canvas is combustible materials, cannot still obtain the material of ideal flame retardant property even if the fully wrapped around canvas of rubberizing.
Current fire retarding conveying band generally mainly by belt carcass (rolled by one or more layers cover canvas of glue constitute), on cover Cap rock, lower caldding layer and side glue composition.Upper and lower coating is generally PVC film, by calendering so that the PVC of melting is in pressure In the gap for easily entering fabric under effect, make to combine well between PVC, while being capable of forming between the PVC and yarn of melting Stronger adhesive layer enhances the interfacial adhesion of the two, and then improves tensile strength.Simultaneously as synthetic fibers (terylene work Industry silk) end is rare, surface is smooth and chemical activity is low, it is more difficult to adhesive bond is established at interface, to promote the viscous of PVC film and fiber Property generally need to be impregnated before being rolled, typically contained in maceration extract can with fibre end base junction close such as-NH2、-OH、- COOH isopolarity group.Presently the most common maceration extract is RFL (resorcinol-formaldehyde resin) maceration extract, and it is suitable for right Cotton, artificial silk, nylon, polyester or glass fabric are handled, this is because containing active hydrogen atom in RF resin, both Crosslinked action can be generated with PVC, and can be with-the NH in fiber2,-OH combine.
But polyester fiber finished product is the supramolecular structure of partially crystallizable, and crystalline portion strand is parallel to each other, and is in mostly Anti conformation, and amorphous region is then in cisoid conformation more, molecules align is quite close, and the active group in maceration extract is difficult to seep Thoroughly to fibrous inside and then in conjunction with the end group inside polyester fiber, this is largely affected between polyester fiber and PVC film Adhesive effect power, affect the peel strength of fire retarding conveying band (terylene fire retardant canvas).
In addition, shrinking percentage is an important performance indexes of polyester industrial fiber, reversible heat expansion is cold with general solid matter Contracting phenomenon is different, after chemical fibre is heated, tends to occur irreversible thermal contraction, and in hot water washing and ironing, contraction is showed It becomes apparent.Industrial yarn (such as cord fabric thread, conveyer belt and conveyer belt) more carries out using shrinking percentage at a high temperature of long-time Performance just increasingly constitute an important evaluation index, the percent thermal shrinkage of the industrial yarn of the prior art is higher, cause by its make The thermal stability of the fabric obtained is poor.
Therefore, it studies active force between a kind of reinforcing fiber and PVC and reduces the method for polyester industrial fiber percent thermal shrinkage in turn Prepare the great realistic meaning of terylene fire retardant canvas that a kind of peel strength is high and percent thermal shrinkage is low.
Summary of the invention
The purpose of the present invention is overcome prior art terylene fire retardant canvas peel strength is not high and percent thermal shrinkage is higher to lack It falls into, the terylene fire retardant canvas and preparation method thereof that a kind of peel strength is high and percent thermal shrinkage is low is provided.
In order to achieve the above objectives, The technical solution adopted by the invention is as follows:
The preparation method of terylene fire retardant canvas is made in the surface calender lamination PVC film of modified polyester industrial yarns woven cloths Terylene fire retardant canvas, terylene fire retardant canvas are the fabrics with flame retardant property, use woven mode through warping by Fire Retardant Industry silk After weaving into woven cloths, then obtained, the preparation side of terylene fire retardant canvas of the invention in the surface calender lamination PVC film of woven cloths Method and the preparation method of prior art terylene fire retardant canvas are essentially identical, the difference is that the material and industrial yarn of industrial yarn Process, the industrial yarn material of the terylene fire retardant canvas of the prior art is common flame retardant polyester, and terylene resistance of the invention The industrial yarn material for firing canvas is modified flame-retardant polyester, heat in the process of the industrial yarn of the terylene fire retardant canvas of the prior art Be rolling step after shaping process, and in the process of the industrial yarn of terylene fire retardant canvas of the invention in heat-setting process and Heat treatment without tension process is additionally arranged between rolling step；
The modified polyester industrial yarns are by the way that modified poly ester melt is carried out solid phase polycondensation thickening, melting, metering, is squeezed Out, it cools down, oil, stretching, made from thermal finalization, heat treatment without tension and winding；
Modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, band trimethylsilyl before the solid phase polycondensation viscosifies The dihydric alcohol and 2- carboxyethyl phenyl hypophosphorous acid of side group successively carry out esterification and polycondensation reaction after mixing；
The structural formula of dihydric alcohol with trimethylsilyl side group is as follows:
In formula, R is-CH2-、-CH(CH3)-or-C ((CH3)2)-；
The heat treatment without tension refers to the space by modified poly ester tow in relaxed state appropriate Jing Guo certain temperature；
The relaxed state appropriate refers to that the over feed rate(OFR) of winding is 3.0~5.0%；
The certain temperature refers to 200~240 DEG C.
Leaching RFL maceration extract is typically necessary during preparing terylene fire retardant canvas by polyester industrial yarn, RFL maceration extract Effect is the binding force improved between fabric and PVC film, and the present invention uses dihydric alcohol (the 3- front three silicon with trimethylsilyl side group Base -1,2- propylene glycol, 3- trimethylsilyl -3- methyl-1,2- propylene glycol or 3- trimethylsilyl -3,3- dimethyl -1,2- propylene glycol) Polyester is modified, the dihydric alcohol with trimethylsilyl side group can significantly increase the space free volume of modified poly ester, especially It is that the presence of trimethylsilyl in the dihydric alcohol with trimethylsilyl side group can cause the variation of main chain activity, to change chain list Interaction force between member, the distance between molecule chain element can also occur to change accordingly, increase modified poly ester cavity free body Product, empty free volume increase molecule reactive group such as-NH so that in RFL maceration extract2,-OH ,-COOH is heat treated It can be readily diffused into fiber gap in journey, obtain good interface and combine, thus improved viscous between fiber and PVC film Cooperation is used, so that adhesive strength obtains biggish raising, and then improves the peel strength of terylene fire retardant canvas, such as using other leachings Stain liquid, empty free volume increase similarly can also improve the peel strength of terylene fire retardant canvas.
The present invention also reduces the shrinking percentage of polyester industrial fiber by the mutual cooperation of heat treatment temperature and over feed rate(OFR) Guarantee the performance of polyester industrial squeeze, fiber is in heat treatment, and macromolecular chain folded chain easy to form in amorphous area has Conducive to the further growth of crystal grain, crystallinity is increased at this time, and along with the raising of crystallinity, fiber can generate a certain amount of receipts On the one hand contracting, the present invention eliminate influence of the high elastic deformation to winding, on the other hand eliminate crystallinity by improving over feed rate(OFR) The influence of the contraction of fiber during raising.
As a preferred technical scheme:
The preparation method of terylene fire retardant canvas as described above, the synthesis step of the dihydric alcohol with trimethylsilyl side group It is as follows:
(1) raw material alkene, peracetic acid and methylene chloride are mixed by the molar ratio of 1:5~10:10~15, at 35~40 DEG C 5~8h is reacted under the conditions of temperature, when reaction, accompanies by stirring, removes solvent after reaction, it is purified be refining to obtain front three silicon Base epoxidation of propylene object；
(2) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object are mixed, under agitation heating water bath to 80~85 DEG C, insulation reaction l0~15min is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain band front three silicon The dihydric alcohol of base side group, the concentrated sulfuric acid is the sulfuric acid of mass concentration 70%, when reaction starts, trimethylsilyl epoxidation of propylene object Molar ratio with water is 1:20~40, and the quality of the concentrated sulfuric acid accounts for the 0.1~0.15% of the sum of mixture quality；
R is-CH (CH in the structural formula of the dihydric alcohol with trimethylsilyl side group3)-and-C ((CH3)2)-when, the original Material alkene corresponds to 3- trimethylsilyl -3- metering system and 3- trimethylsilyl -3,3- dimethyl allene.
The preparation method of terylene fire retardant canvas as described above, the preparation step of modified poly ester before the solid phase polycondensation viscosifies It is as follows:
(1) esterification；
By terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with trimethylsilyl side group with being slurried Catalyst, delustering agent and stabilizer is added after mixing in material, and pressurization carries out esterification, moulding pressure in nitrogen atmosphere For normal pressure~0.3MPa, the temperature of esterification is 250~260 DEG C, when the water quantity of distillate in esterification reaches theoretical value It is esterification terminal when 90% or more；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure 30~ Absolute pressure 500Pa being steadily evacuated to by normal pressure in 50min hereinafter, reaction temperature is 250~260 DEG C, the reaction time is 30~ 50min then proceedes to vacuumize, and carries out the polycondensation reaction of high vacuum stage of Fig, reaction pressure is made to be further reduced to absolute pressure For 100Pa hereinafter, reaction temperature is 270~282 DEG C, the reaction time is 50~90min.
The preparation method of terylene fire retardant canvas as described above, the terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl The molar ratio of phosphoric acid and the dihydric alcohol with trimethylsilyl side group is 1:1.2~2.0:0.03~0.05:0.02~0.03, described to urge The additional amount of agent, delustering agent and stabilizer be respectively 0.03~0.05wt% of terephthalic acid (TPA) additional amount, 0.20~ 0.25wt% and 0.01~0.05wt% (mass percent).The additional amount of dihydric alcohol of the present invention with trimethylsilyl side group is not Be limited to this, those skilled in the art can actual conditions be adjusted, but adjust amplitude should not be too large, additive amount is excessive big to polyester The regularity destruction of molecular structure is too big, excessive to the crystallinity and Effect on Mechanical Properties of fiber, is unfavorable for the production of fiber And application, additive amount is too low, then effect (acting on the raising of adhesive strength) is unobvious.
The preparation method of terylene fire retardant canvas as described above, the catalyst are antimony oxide, antimony glycol or vinegar Sour antimony, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or Trimethyl phosphite.
The preparation method of terylene fire retardant canvas as described above, the inherent viscosity of modified poly ester after the solid phase polycondensation viscosifies For 1.0~1.2dL/g.
The preparation method of terylene fire retardant canvas as described above, the space of the certain temperature refer to it is a pair of arranged in parallel and Space between non-coplanar hot plate, hot plate are located in FDY equipment between last group of setting roller and take-up roll；Along modified poly- The length of the traffic direction of ester tow, two hot plates is 3.0~4.0m, and the both ends of two hot plates flush；Modified poly ester tow is warm from two When passing through among plate, the distance between two hot plates are 5~10mm；The present invention is (i.e. described certain by control hot plate temperature Temperature) guarantee that macromolecular rearrangement can obtain energy, the length of hot plate is controlled to guarantee enough crystallization times, control tow and heat The distance of plate is to guarantee that the efficiency being heat-treated, the mutual coordinated of three improve the integrality of fiber crystallization, and then reduces fiber Thermal contraction in application process, wherein hot plate temperature is too low, it is difficult to guarantee that macromolecular rearrangement can obtain enough energy；Heat Plate temperature is excessively high to destroy former established structure；Hot plate length is too short, and crystallization time is too short, influences the complete of fiber crystallization Property, influence fiber percent thermal shrinkage；The too long efficiency decline manufacturing apparatus waste of hot plate length；Tow is too small at a distance from hot plate to be easy to make It is contacted at the direct of tow；Tow excessive thermal efficiency at a distance from hot plate reduces；
Spacing between last group of setting roller and take-up roll is 300~400mm；Two hot plates and last group of thermal finalization Spacing between roller is 200~300mm.
The preparation method of terylene fire retardant canvas as described above, the spinning technology parameter of the modified polyester industrial yarns is such as Under:
It stretches, the technological parameter of thermal finalization are as follows:
The temperature of the calender lamination is 165~170 DEG C, and pressure is 5~5.5MPa, and the time is 75~90s；The PVC Film is located at the double-sided surface of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 0.40~0.75mm.
Preparation process of the invention is not limited to that, only enumerates a kind of feasible technical solution herein.Concrete technology ginseng Number is also not limited to this, can be adjusted according to actual needs.
The present invention also provides terylene fire retardant canvas made from a kind of preparation method using terylene fire retardant canvas as described above, With lamination layer structure, mainly it is made of modified polyester industrial yarns woven layer and PVC film layer；
The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment, 2- carboxyethyl phenyl hypophosphorous acid With the dihydric alcohol segment with trimethylsilyl side group.
As a preferred technical scheme:
Terylene fire retardant canvas as described above, the filament number of modified polyester industrial yarns are 3.0~5.0dtex, and fracture is strong Degree >=7.5cN/dtex, line density deviation ratio be ± 1.5%, breaking strength CV value≤3.0%, elongation at break be 18.0~ 20.0%, extension at break CV value≤8.0%, the present invention changes polyester by introducing the dihydric alcohol with trimethylsilyl side group Property, the above-mentioned mechanical property of obtained fiber does not decline, suitable with the prior art, modified polyester industrial yarns 190 DEG C × Dry-hot shrinkage under the conditions of 15min × 0.01cN/dtex is 2.5~3.3%, and internet pricing is (5~8) ± 2/m, and LOI is 30~34, the dry-hot shrinkage of the lower shrinkage type polyester industrial fiber of the prior art in this test condition is 3.5~4.3%, right Than can be seen that the percent thermal shrinkage present invention significantly reduces polyester industrial fiber；
The grammes per square metre of terylene fire retardant canvas is 500~800g/m2, flaming combustion time is less than or equal to 1.5s, when flameless combustion Between be less than or equal to 2.5s, adhesive strength is 50~60N/cm, and peel strength >=8.5N/cm, longitudinal tensile strength is more than or equal to 281N/cm, transverse tensile strength are more than or equal to 285N/cm, and longitudinal elongation at break rate is 6.3~6.5%, transverse breakage elongation It is 5.6~6.0%, use temperature range is -30 DEG C~+60 DEG C, resistance to hydrostatic pressure value >=90KPa, and resistance to hydrostatic pressure value is that fabric exists Under the hydraulic pressure effect persistently risen, pressure value when infiltration, rub resistance time numerical value >=3000 time, rub resistance number has just taken place Value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place, and terylene fire retardant canvas of the invention glues The terylene fire retardant canvas that intensity, peel strength and tensile strength are much higher than the prior art is closed, is primarily due to the present invention to terylene The material of fire retardant canvas is improved, and the dihydric alcohol segment with trimethylsilyl side group, band three are introduced in polyester molecule chain The presence of trimethylsilyl can cause the variation of main chain activity in the dihydric alcohol of first silicon substrate side group, thus between changing chain element Interaction force, the distance between molecule chain element can also occur to change accordingly, as a result lead to polymer cavity free volume Increase, empty free volume increase can make molecule reactive group such as-NH in RFL maceration extract2,-OH etc. is in heat treatment process In diffuse into fiber gap, obtain good interface and combine, thus improve the adhesive effect between fiber and PVC film, So that adhesive strength, peel strength and tensile strength obtain certain raising.
Invention mechanism:
Macromolecular chain in polymer is not closely to pile up completely, always with the presence of gap between macromolecular chain, this Portion void volume is free volume.It penetrates into small molecule inside macromolecule, to have foot in macromolecule or between macromolecule Enough big gaps, so pore size (the i.e. ruler of free volume in the permeability and diffusivity of small molecule and macromolecular structure It is very little) it is related, in a certain range, the size of free volume is bigger, and the permeability of small molecule is higher, and diffusivity is better.Free body Product is divided into empty free volume and slit free volume again, and empty free body has bigger bulk compared with slit free volume, Promotion for the permeability of small molecule, empty free volume are more obvious compared with slit free volume effect.
The size and type of free volume depend primarily on the structure of polymer, and the principal element for influencing polymer architecture is Steric hindrance, side group size, side group structure etc..When position a certain on main polymer chain is replaced by side group, necessarily cause main chain The variation of activity, to change the interaction force of chain and interchain, chain can also occur to change accordingly at a distance from interchain, As a result lead to the variation of cohesive energy and free volume, polarity, size, length of the substituent group on polymer side chain etc. are to strand Rigid, intermolecular interaction so that the fractional free volume of polymer architecture all have a certain impact, therefore, substituent group The effect that difference generates is different, and the permeability and separation performance for often leading to polymer is also different.
The present invention is obviously improved the fire-retardant sail of terylene by introducing the dihydric alcohol with trimethylsilyl side group in polyester molecule chain The structural formula of the adhesive strength of cloth, the dihydric alcohol with trimethylsilyl side group is as follows:
In formula, R is-CH2(dihydric alcohol with trimethylsilyl side group is 3- trimethylsilyl -1,2- propylene glycol),-CH (CH3)- (dihydric alcohol with trimethylsilyl side group is 3- trimethylsilyl -3- methyl-1,2- propylene glycol) or-C ((CH3)2)-(band trimethylsilyl The dihydric alcohol of side group is 3- trimethylsilyl -3,3- dimethyl -1,2- propylene glycol)；
For ethylene glycol straight chain molecule, the C atom on main chain is arranged in indention one on the other, when on main chain some H atom on methylene is by methyl (- CH3) when replacing, C atom and main chain C atom on substituent group not in the same plane, in It is that four on the C of center sp3 hybridized orbit is Chong Die with the unoccupied orbital on four C atoms around respectively, formation four is identical σ key, arranged in positive tetrahedron, four carbon atom is located at four vertex of positive tetrahedron, when three hydrogen of methyl are into one When step is replaced by methyl or trimethylsilyl, it is capable of forming a bigger tetrahedral structure, this is in the arrangement of positive tetrahedron shape The strand that strand is arranged relative to indention, empty free volume significantly increase very much, can significantly improve small point The permeability and diffusivity of son are conducive to atom further, since the bond distance of carbon silicon bonds is greater than the bond distance of carbon-carbon bond in trimethylsilyl It rotates freely, and then is conducive to increase empty free volume；And when the H atom on main chain on some methylene is replaced by long-chain branch When base replaces, what is mainly increased is slit free volume, and increase amplitude is smaller, permeability and diffusible promotion to small molecule Effect is limited, simultaneously because the rigidity for chain substituent of drawing money on credit is smaller, entanglement is easy to happen between strand, is unfavorable for free volume Increase.
The presence of trimethylsilyl can cause the variation of main chain activity in dihydric alcohol with trimethylsilyl side group, to change Interaction force between chain element, the distance between molecule chain element can also occur to change accordingly, cause the cavity of polyester from By the increase of volume.Compared with short-chain branch substituent group (such as methyl, ethyl group), trimethylsilyl occupies biggish space bit It sets, bigger free volume will be obtained in the mode of strand arrangement；Compared with chain substituent of drawing money on credit, one side trimethylsilyl Increase be empty free volume, and draw money on credit chain substituent increase be slit free volume, another aspect trimethylsilyl it is rigid Property be greater than and draw money on credit chain substituent, reduce the entanglement between strand, thus trimethylsilyl relatively draws money on credit chain substituent in strand There are more free volumes in the mode of arrangement.Empty free volume increases the active base of molecule so that in RFL maceration extract Group such as-NH2,-OH ,-COOH can diffuse into fiber gap during heat treatment, obtain good interface and combine, because And the adhesive effect between fiber and PVC film is improved, so that adhesive strength, peel strength and tensile strength obtain certain mention It is high.
In addition, the present invention has adjusted the processing technology of polyester industrial fiber also to reduce the percent thermal shrinkage of polyester industrial fiber；
Fiber is in post-processing stretching process, and due to the effect of mechanical stress, fiber orientation degree is significantly increased and has Certain crystallinity, to make elongate fiber and total deformation work reduce, during stretching, although the big portion of fibrogenic deformation Dividing is expendable plastic deformation under room temperature, and often because crystallization is fixed, however some can be in room temperature It is lower to restore because of the relaxation of tensile stress, or reply can be shunk in subsequent heat-treated, in the application process of fiber In this shrink that reply be that the shrinking percentage of fiber will be largely affected by performance (such as security performance, endurance quality of fiber Deng), it is assumed that the fiber is used as tire cord, and in use, cord fabric thread is stretched repeatedly, compressed, is bent tire, causes Tire is heated, leads to curtain linear shrinkage creep, but when curtain linear shrinkage is excessive may knife cord fabric delamination, and then lead to tire Disintegrate, this carrys out greatly hidden danger to using of seat belts for tire.
It is the shrinking percentage for reducing polyester industrial fiber as much as possible at present during the spin-drawing of polyester industrial fiber, It generally requires to carry out nervous thermal finalization (carrying out shaping fiber under some tension using setting roller) after carrying out multiple tracks stretching, To overfeeding of the over feed rate(OFR) for 1~2% is wound with after nervous thermal finalization, by carrying out nervous thermal finalization to fiber, in certain temperature Under conditions of degree and some tension, the mobility of molecule segment is improved, so that intermolecular combination obtains even closer, raising fiber Average grain size and crystallinity, to drop low-fiber shrinking percentage, but since fiber has certain height during stretching Deformation is played, elastic recovery can be generated in the case where tension reduces, therefore, it is fixed that the speed of winding head has to be lower than last group heat The speed of type roller needs certain over feed rate(OFR), is shunk, is expired with guaranteeing that the silk after stretching obtains a degree of low-tension The final product quality of meaning and package prevent package from causing turned-down edge because of overtension, over feed rate(OFR) need to control in a certain range (1~ 2%) it, crosses conference and adverse effect is generated to final product quality and package.Although can be to a certain extent by nervous thermal finalization+overfeeding Reduce shrinking percentage, but in nervous heat-setting process, due to the length of fiber be fixed it is immutable, it is suppressed that macromolecular chain Folding, thus the rate of grain growth is restricted, and causes to crystallize existing defects (crystallinity increases less), and only pass through Control overfeeding can not reduce crystal defect, when this will lead to fiber obtained and is heat-treated in application process, fiber it is big Strand and segment have higher activity, are easy to produce deorientation, cause fiber that a certain amount of shrink occurs and (shrink Rate is larger).
In fact, the thermal finalization mode of fiber is not only nervous thermal finalization, further includes relaxation heat setting.Relaxation heat setting is again Referred to as free shrink thermal finalization is fiber under complete no-station pole canopy or the lesser situation of tension, by certain temperature to fiber Be heat-treated, under the conditions of relaxation heat setting, fiber can free shrink, the macromolecular chain folding easy to form in amorphous area Chain is conducive to the further growth of crystal grain, in addition more abundant heat treatment time, therefore after heat treatment without tension, the knot of fiber Brilliant degree increases more (compared to nervous thermal finalization), to make that fibrous inside high elastic deformation is restored while internal stress is filled Divide relaxation, so that fibrogenic contraction reply is smaller when being heat-treated in application process.Current relaxation heat is fixed Type be mainly used for polyester staple fiber carry out thermal finalization processing, heat treatment temperature is lower (130 DEG C or so), heat treatment time compared with It is long, it is difficult to be suitable for long filament and produce.
The present invention by the way that the over feed rate(OFR) that polyester tow is wound is promoted to 3~5% in the process of polyester industrial fiber, Hot plate arranged in parallel above and below a pair of is set between one of setting roller last in FDY equipment and take-up roll simultaneously, by polyester Tow passes through among two hot plates, improves the crystallinity of polyester tow, has restored the high elastic deformation inside polyester tow, so that Polyester tow internal stress obtains a certain amount of relaxation, and then reduces polyester industrial fiber when being heat-treated in application process and send out Raw contraction is replied.The present invention reduces the receipts of polyester industrial fiber by the mutual cooperation of heat treatment temperature and higher over feed rate(OFR) Shrinkage, fiber is in heat treatment, and macromolecular chain folded chain easy to form in amorphous area is conducive to the further life of crystal grain Long, crystallinity increases at this time, and along with the raising of crystallinity, fiber can generate a certain amount of contraction, and the present invention is super by improving The rate of feeding, on the one hand eliminates influence of the high elastic deformation to winding, on the other hand eliminates the receipts of fiber during crystallinity improves The influence of contracting.In addition, the present invention is by the mutual cooperation of heat treatment temperature, hot plate length and tow and hot plate apart from three, one Aspect overcomes the defect that prior art heat treatment without tension is not suitable for long filament production, on the other hand, improves fiber crystallization Integrality improves the stability of fiber size, reduces the thermal contraction in its application process.
The utility model has the advantages that
(1) preparation method of a kind of terylene fire retardant canvas of the invention, simple process and low cost, by the polyester It introduces the dihydric alcohol with trimethylsilyl side group to be modified polyester, increases the empty free volume of polyester, soaked with subsequent RF L Stain technique cooperates the adhesive strength for significantly improving canvas；
(2) preparation method of a kind of terylene fire retardant canvas of the invention passes through heat treatment temperature and higher over feed rate(OFR) It cooperates, improves the integrality of fiber crystallization, reduce the thermal contraction in its application process；
(3) a kind of terylene fire retardant canvas of the invention, adhesive strength is good, and good mechanical property has a extensive future.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
The preparation method of terylene fire retardant canvas, steps are as follows:
(1) modified poly ester is prepared；
(1.1) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and the 3- tri- for being 1:1.2:0.03:0.02 by molar ratio First silicon substrate -1,2-PD is made into slurry, antimony oxide, titanium dioxide and triphenyl phosphate is added after mixing, in nitrogen Atmosphere encloses middle pressurization and carries out esterification, and moulding pressure is normal pressure, and the temperature of esterification is 250 DEG C, when in esterification Be esterification terminal when water quantity of distillate reaches the 95% of theoretical value, antimony oxide, titanium dioxide and triphenyl phosphate plus Enter 0.03wt%, 0.20wt% and 0.01wt% that amount is respectively terephthalic acid (TPA) additional amount；
(1.2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 40min The interior absolute pressure that is steadily evacuated to by normal pressure is 480Pa, and reaction temperature is 250 DEG C, reaction time 30min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 80Pa, reaction temperature 270 DEG C, reaction time 50min, the number-average molecular weight of modified poly ester obtained is 24000, molecular weight distributing index 1.9；
(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.0dL/g, the polyester tow that it is 5% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar same The space between hot plate that Shi Wendu is 200 DEG C, hot plate are located in FDY equipment between last group of setting roller and take-up roll, Along the traffic direction of polyester tow, the length of two hot plates is 3.0m, and the both ends of two hot plates flush, and polyester tow is among two hot plates Across when, the distance between two hot plates are 5mm, and spacing between last group of setting roller and take-up roll is 300mm, two Spacing between hot plate and last group of setting roller is 200mm；Spinning technology parameter is as follows: each area's temperature of screw rod is 290 DEG C； Spin manifold temperature is 295 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 75%；Cross air blasting wind speed For 0.5m/s；Winding speed is 3268m/min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 480m/min；One roller Temperature is 23 DEG C；Two roller speeds are 500m/min；Two roll temperatures are 80 DEG C；Three roller speeds are 1800m/min；Three roll temperatures are 100℃；Four roller speeds are 2800m/min；Four roll temperatures are 200 DEG C；Five roller speeds are 2800m/min；Five roll temperatures are 200 ℃；Six roller speeds are 3440m/min；Six roll temperatures are 150 DEG C；
The filament number of modified polyester industrial yarns is 3.0dtex, breaking strength 8.4cN/dtex, line density deviation ratio Be -1.3%, breaking strength CV value be 2.5%, elongation at break 18.0%, extension at break CV value be 7.2%, 190 DEG C × Dry-hot shrinkage under the conditions of 15min × 0.01cN/dtex is 2.5%, and internet pricing is 3/m, LOI 30；
(3) modified polyester industrial yarns are weaved into Cheng Buhou in the surface calender lamination PVC of modified polyester industrial yarns woven cloths The terylene fire retardant canvas that fabric construction is 1/1 plain weave is made in film, wherein weaving is carried out using biaxial warp knitting machine, modified Indulging close for polyester industrial fiber woven cloths is 3.8 coils/cm, and close cross is 7.3 coils/cm, surface density 42.0g/m2, pasted in calendering Primary coat is also carried out before closing, primary coat refers to paste PVC (paste PVC, phthalic acid diethyl containing adhesive at 30 DEG C Ester, zinc-tin stabilizer, toluene diisocynate poly- isocyanurate weight ratio be 100:50:1:0.3 mixture, paste PVC Model P440, the degree of polymerization 1500) be coated in modified polyester industrial yarns woven cloths after, the precuring 35s at 140 DEG C, and Carrying out PVC calender lamination in modified polyester industrial yarns woven cloths after precuring processing afterwards, the temperature of calender lamination is 165 DEG C, Pressure is 5.0MPa, time 75s；PVC film is located at the double-sided surface of modified polyester industrial yarns woven cloths, the thickness of unilateral PVC film Degree is 0.4mm.
Terylene fire retardant canvas has lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer, The grammes per square metre of terylene fire retardant canvas is 500g/m2, flaming combustion time 1.2s, glowing time 2.0s, adhesive strength is 50N/cm, peel strength 8.5N/cm, longitudinal tensile strength 281N/cm, transverse tensile strength 287N/cm, longitudinal fracture Elongation is 6.3%, and transverse breakage elongation is 5.8%, and use temperature range is -30 DEG C~+60 DEG C, and resistance to hydrostatic pressure value is 90KPa, resistance to hydrostatic pressure value are fabric under the hydraulic pressure effect of lasting rising, and pressure value when infiltration, rub resistance has just taken place Secondary numerical value is 3000 times, and rub resistance time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.
Comparative example 1
The preparation method of terylene fire retardant canvas, preparation method and embodiment 1 are almost the same, the difference is that in step (1.1) 3- trimethylsilyl -1,2-PD is not added, and the filament number of polyester industrial yarn obtained is 3.0dtex, and breaking strength is 8.5cN/dtex, line density deviation ratio are -1.3%, and breaking strength CV value is 2.5%, and elongation at break 18.0%, fracture is stretched Long CV value is 7.5%, and dry-hot shrinkage under the conditions of 190 DEG C × 15min × 0.01cN/dtex is 2.5%, internet pricing 3 A/m, LOI 30；
Under preparation condition same as Example 1, the grammes per square metre of terylene fire retardant canvas as made from the polyester industrial yarn is 500g/m2, flaming combustion time 1.2s, glowing time 2.0s, adhesive strength 32N/cm, peel strength is 6.1N/cm, longitudinal tensile strength 262N/cm, transverse tensile strength 265N/cm, longitudinal elongation at break rate 6.5% are horizontal It is 5.7% to elongation at break, use temperature range is -20 DEG C~+50 DEG C, and resistance to hydrostatic pressure value is 64KPa, and resistance to hydrostatic pressure value is Pressure value when infiltration has just taken place under the hydraulic pressure effect of lasting rising in fabric, and rub resistance time numerical value is 2000 times, antifriction Wiping time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.It can be sent out with the comparison of embodiment 1 It is existing, since 3- trimethylsilyl -1,2-PD of the invention can increase the empty free volume of polyester, empty free volume Increase molecule reactive group such as-NH so that in diethyl phthalate during following process2,-OH ,-COOH is in warm It can be diffused into fiber gap in treatment process, obtain good interface and combine, thus improved between fiber and PVC film Adhesive effect, so that adhesive strength, peel strength and tensile strength obtain certain raising.
Comparative example 2
The preparation method of terylene fire retardant canvas, preparation method and embodiment 1 are almost the same, the difference is that in step (1.3) 3- trimethylsilyl -1,2-PD is replaced to be washed under preparation condition same as Example 1 by this using 1,2 dodecanediol The grammes per square metre of terylene fire retardant canvas made from synthetic fibre industrial yarn is 500g/m2, flaming combustion time 1.2s, glowing time is 2.0s, adhesive strength 34N/cm, peel strength 6.2N/cm, longitudinal tensile strength 240N/cm, transverse tensile strength are 241N/cm, longitudinal elongation at break rate 6.3%, transverse breakage elongation are 5.8%, and use temperature range is -20 DEG C~+50 DEG C, resistance to hydrostatic pressure value is 57KPa, and resistance to hydrostatic pressure value is fabric under the hydraulic pressure effect of lasting rising, when infiltration has just taken place Pressure value, rub resistance time numerical value is 2000 times, and rub resistance time numerical value is fabric under continuous frictional effect, and change has just taken place Rubbing number when change.With the comparison of embodiment 1 it can be found that compared to slit free volume, trimethylsilyl -1 3- of the invention, It is living that the empty free volume that 2- propylene glycol increases is more advantageous to the molecule during making following process in diethyl phthalate Sprinkle group such as-NH2,-OH ,-COOH can diffuse into fiber gap during heat treatment, obtain good interface knot It closes, thus improves the adhesive effect between fiber and PVC film, so that adhesive strength, peel strength and tensile strength obtain centainly Raising.
Embodiment 2
The preparation method of terylene fire retardant canvas, steps are as follows:
(1) modified poly ester is prepared；
(1.1) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and the 3- for being 1:1.4:0.032:0.022 by molar ratio Trimethylsilyl -1,2-PD is made into slurry, antimony glycol, titanium dioxide and triphenyl phosphate is added after mixing, in nitrogen Atmosphere encloses middle pressurization and carries out esterification, and moulding pressure 0.2MPa, the temperature of esterification is 255 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 95% of theoretical value, antimony glycol, titanium dioxide and triphenyl phosphate plus Enter 0.035wt%, 0.22wt% and 0.02wt% that amount is respectively terephthalic acid (TPA) additional amount；
(1.2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 44min The interior absolute pressure that is steadily evacuated to by normal pressure is 500Pa, and reaction temperature is 252 DEG C, reaction time 32min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 90, and reaction temperature is 270 DEG C, Reaction time is 55min, and the number-average molecular weight of modified poly ester obtained is 24800, molecular weight distributing index 1.9；
(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.0dL/g, the polyester tow that it is 5% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar same The space between hot plate that Shi Wendu is 207 DEG C, hot plate are located in FDY equipment between last group of setting roller and take-up roll, Along the traffic direction of polyester tow, the length of two hot plates is 3.2m, and the both ends of two hot plates flush, and polyester tow is among two hot plates Across when, the distance between two hot plates are 6mm, and spacing between last group of setting roller and take-up roll is 311mm, two Spacing between hot plate and last group of setting roller is 220mm；
Spinning technology parameter is as follows: each area's temperature of screw rod is 290 DEG C；Spin manifold temperature is 295 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 75%；Cross air blasting wind speed is 0.5m/s；Winding speed is 3268m/ min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 480m/min；One roll temperature is 23 DEG C；Two roller speeds are 500m/ min；Two roll temperatures are 80 DEG C；Three roller speeds are 1800m/min；Three roll temperatures are 100 DEG C；Four roller speeds are 2800m/min；Four Roll temperature is 200 DEG C；Five roller speeds are 2800m/min；Five roll temperatures are 200 DEG C；Six roller speeds are 3440m/min；Six roller temperatures Degree is 150 DEG C；
The filament number of modified polyester industrial yarns is 3.0dtex, breaking strength 8.2cN/dtex, and line density deviation ratio is 1.3%, breaking strength CV value be 2.6%, elongation at break 18.0%, extension at break CV value be 7.2%, 190 DEG C × Dry-hot shrinkage under the conditions of 15min × 0.01cN/dtex is 2.6%, and internet pricing is 3/m, LOI 31；
(3) modified polyester industrial yarns are weaved into Cheng Buhou in the surface calender lamination PVC of modified polyester industrial yarns woven cloths The terylene fire retardant canvas that fabric construction is 1/1 plain weave is made in film, wherein weaving is carried out using biaxial warp knitting machine, modified Indulging close for polyester industrial fiber woven cloths is 3.6 coils/cm, and close cross is 7.1 coils/cm, surface density 38.0g/m2, pasted in calendering Primary coat is also carried out before closing, primary coat refers to paste PVC (paste PVC, phthalic acid diethyl containing adhesive at 50 DEG C Ester, zinc-tin stabilizer, toluene diisocynate poly- isocyanurate weight ratio be 100:60:2:2.0 mixture, paste PVC Model P440, the degree of polymerization 1500) be coated in modified polyester industrial yarns woven cloths after, the precuring 45s at 160 DEG C, and PVC calender lamination is carried out in precuring treated modified polyester industrial yarns woven cloths afterwards, the temperature of calender lamination is 165 DEG C, pressure 5.2MPa, time 75s；PVC film is located at the double-sided surface of modified polyester industrial yarns woven cloths, unilateral PVC film With a thickness of 0.4mm.
Terylene fire retardant canvas has lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer, The grammes per square metre of terylene fire retardant canvas is 500g/m2, flaming combustion time 1.3s, glowing time 2.0s, adhesive strength is 52N/cm, peel strength 8.6N/cm, longitudinal tensile strength 282N/cm, transverse tensile strength 285N/cm, longitudinal fracture Elongation is 6.3%, and transverse breakage elongation is 5.6%, and use temperature range is -30 DEG C~+60 DEG C, and resistance to hydrostatic pressure value is 90KPa, resistance to hydrostatic pressure value are fabric under the hydraulic pressure effect of lasting rising, and pressure value when infiltration, rub resistance has just taken place Secondary numerical value is 3000 times, and rub resistance time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.
Embodiment 3
The preparation method of terylene fire retardant canvas, steps are as follows:
(1) modified poly ester is prepared；
(1.1) dihydric alcohol with trimethylsilyl side group is prepared；
(1.1.1) is mixed 3- trimethylsilyl -3- metering system, peracetic acid and methylene chloride by the molar ratio of 1:5:10, React 5h under the conditions of 35 DEG C of temperature, when reaction accompanies by stirring, removes solvent after reaction, purified and be refining to obtain three First silicon substrate epoxidation of propylene object；
(1.1.2) mixes water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object, under agitation heating water bath to 80 DEG C, insulation reaction 10min is cooled to room temperature after reaction, and neutralized, distillation, separation and purification are obtained as shown in formula (I) Dihydric alcohol with trimethylsilyl side group, the R in formula (I) are-CH (CH3)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, instead When should start, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:20, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality 0.1%；
(1.2) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and the band for being 1:1.5:0.035:0.023 by molar ratio The dihydric alcohol of trimethylsilyl side group is made into slurry, antimony glycol, titanium dioxide and trimethyl phosphate is added after mixing, in nitrogen Atmosphere encloses middle pressurization and carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 255 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 95% of theoretical value, antimony glycol, titanium dioxide and trimethyl phosphate plus Enter 0.04wt%, 0.23wt% and 0.03wt% that amount is respectively terephthalic acid (TPA) additional amount；
(1.3) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 38min The interior absolute pressure that is steadily evacuated to by normal pressure is 440Pa, and reaction temperature is 251 DEG C, reaction time 33min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 100Pa, reaction temperature 272 DEG C, reaction time 60min, the number-average molecular weight of modified poly ester obtained is 25000, molecular weight distributing index 2.0；
(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.1dL/g, the polyester tow that it is 3.5% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 215 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.3m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 7mm, and the spacing between last group of setting roller and take-up roll is 335mm, the spacing between two hot plates and last group of setting roller are 235mm；
Spinning technology parameter is as follows: each area's temperature of screw rod is 300 DEG C；Spin manifold temperature is 297 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 80%；Cross air blasting wind speed is 0.6m/s；Winding speed is 3300m/ min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 500m/min；One roll temperature is 25 DEG C；Two roller speeds are 700m/ min；Two roll temperatures are 90 DEG C；Three roller speeds are 2000m/min；Three roll temperatures are 120 DEG C；Four roller speeds are 3200m/min；Four Roll temperature is 220 DEG C；Five roller speeds are 3000m/min；Five roll temperatures are 220 DEG C；Six roller speeds are 3420m/min；Six roller temperatures Degree is 170 DEG C；
The filament number of modified polyester industrial yarns is 3.5dtex, breaking strength 8.2cN/dtex, and line density deviation ratio is 1.3%, breaking strength CV value be 2.7%, elongation at break 19.0%, extension at break CV value be 7.4%, 190 DEG C × Dry-hot shrinkage under the conditions of 15min × 0.01cN/dtex is 2.7%, and internet pricing is 3/m, LOI 32；
(3) modified polyester industrial yarns are weaved into Cheng Buhou in the surface calender lamination PVC of modified polyester industrial yarns woven cloths The terylene fire retardant canvas that fabric construction is 1/1 plain weave is made in film, wherein weaving is carried out using biaxial warp knitting machine, modified Indulging close for polyester industrial fiber woven cloths is 3.8 coils/cm, and close cross is 7.3 coils/cm, surface density 42.0g/m2, pasted in calendering Primary coat is also carried out before closing, primary coat refers to paste PVC (paste PVC, phthalic acid diethyl containing adhesive at 40 DEG C Ester, zinc-tin stabilizer, toluene diisocynate poly- isocyanurate weight ratio be 100:55:1.5:1.2 mixture, paste The model P440 of PVC, the degree of polymerization 1500) be coated in modified polyester industrial yarns woven cloths after, the precuring 40s at 150 DEG C, PVC calender lamination is then carried out in precuring treated modified polyester industrial yarns woven cloths, the temperature of calender lamination is 165 DEG C, pressure 5.5MPa, time 75s；PVC film is located at the double-sided surface of modified polyester industrial yarns woven cloths, unilateral PVC film With a thickness of 0.6mm.
Terylene fire retardant canvas has lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer, The grammes per square metre of terylene fire retardant canvas is 600g/m2, flaming combustion time 1.3s, glowing time 2.2s, adhesive strength is 52N/cm, peel strength 8.2N/cm, longitudinal tensile strength 286N/cm, transverse tensile strength 290N/cm, longitudinal fracture Elongation is 6.3%, and transverse breakage elongation is 5.6%, and use temperature range is -20 DEG C~+60 DEG C, and resistance to hydrostatic pressure value is 92KPa, resistance to hydrostatic pressure value are fabric under the hydraulic pressure effect of lasting rising, and pressure value when infiltration, rub resistance has just taken place Secondary numerical value is 3100 times, and rub resistance time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.
Embodiment 4
The preparation method of terylene fire retardant canvas, steps are as follows:
(1) modified poly ester is prepared；
(1.1) dihydric alcohol with trimethylsilyl side group is prepared；
(1.1.1) is mixed 3- trimethylsilyl -3- metering system, peracetic acid and methylene chloride by the molar ratio of 1:10:15, React 8h under the conditions of 40 DEG C of temperature, when reaction accompanies by stirring, removes solvent after reaction, purified and be refining to obtain three First silicon substrate epoxidation of propylene object；
(1.1.2) mixes water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object, under agitation heating water bath to 85 DEG C, insulation reaction 15min is cooled to room temperature after reaction, and neutralized, distillation, separation and purification are obtained as shown in formula (I) Dihydric alcohol with trimethylsilyl side group, the R in formula (I) are-CH (CH3)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, instead When should start, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:40, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality 0.15%；
(1.2) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and the band for being 1:1.5:0.04:0.024 by molar ratio The dihydric alcohol of trimethylsilyl side group is made into slurry, antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing, in nitrogen Atmosphere encloses middle pressurization and carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 255 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 95% of theoretical value, antimony acetate, titanium dioxide and Trimethyl phosphite plus Enter 0.04wt%, 0.25wt% and 0.03wt% that amount is respectively terephthalic acid (TPA) additional amount；
(1.3) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30min The interior absolute pressure that is steadily evacuated to by normal pressure is 460Pa, and reaction temperature is 253 DEG C, reaction time 35min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 88Pa, reaction temperature 274 DEG C, reaction time 65min, the number-average molecular weight of modified poly ester obtained is 25500, molecular weight distributing index 2.2；
(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.1dL/g, the polyester tow that it is 3.3% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 222 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.4m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 8mm, and the spacing between last group of setting roller and take-up roll is 346mm, the spacing between two hot plates and last group of setting roller are 250mm；
Spinning technology parameter is as follows: each area's temperature of screw rod is 300 DEG C；Spin manifold temperature is 297 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 80%；Cross air blasting wind speed is 0.6m/s；Winding speed is 2650m/ min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 500m/min；One roll temperature is 25 DEG C；Two roller speeds are 700m/ min；Two roll temperatures are 90 DEG C；Three roller speeds are 2000m/min；Three roll temperatures are 120 DEG C；Four roller speeds are 3200m/min；Four Roll temperature is 220 DEG C；Five roller speeds are 3000m/min；Five roll temperatures are 220 DEG C；Six roller speeds are 2740m/min；Six roller temperatures Degree is 170 DEG C；
The filament number of modified polyester industrial yarns is 3.5dtex, breaking strength 8.0cN/dtex, and line density deviation ratio is 1.3%, breaking strength CV value be 2.8%, elongation at break 19.0%, extension at break CV value be 7.4%, 190 DEG C × Dry-hot shrinkage under the conditions of 15min × 0.01cN/dtex is 2.7%, and internet pricing is 5/m, LOI 32；
(3) modified polyester industrial yarns are weaved into Cheng Buhou in the surface calender lamination PVC of modified polyester industrial yarns woven cloths The terylene fire retardant canvas that fabric construction is 1/1 plain weave is made in film, weaves and the technological parameter of primary coat is the same as embodiment 1, calender lamination Temperature be 165 DEG C, pressure 5.5MPa, time 75s；PVC film is located at the double-sided surface of modified polyester industrial yarns woven cloths, Unilateral PVC film with a thickness of 0.6mm.
Terylene fire retardant canvas has lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer, The grammes per square metre of terylene fire retardant canvas is 600g/m2, flaming combustion time 1.3s, glowing time 2.3s, adhesive strength is 53N/cm, peel strength 8.3N/cm, longitudinal tensile strength 287N/cm, transverse tensile strength 290N/cm, longitudinal fracture Elongation is 6.3%, and transverse breakage elongation is 5.6%, and use temperature range is -20 DEG C~+60 DEG C, and resistance to hydrostatic pressure value is 93KPa, resistance to hydrostatic pressure value are fabric under the hydraulic pressure effect of lasting rising, and pressure value when infiltration, rub resistance has just taken place Secondary numerical value is 3100 times, and rub resistance time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.
Embodiment 5
The preparation method of terylene fire retardant canvas, steps are as follows:
(1) modified poly ester is prepared；
(1.1) dihydric alcohol with trimethylsilyl side group is prepared；
(1.1.1) is mixed 3- trimethylsilyl -3- metering system, peracetic acid and methylene chloride by the molar ratio of 1:10:10, React 6h under the conditions of 36 DEG C of temperature, when reaction accompanies by stirring, removes solvent after reaction, purified and be refining to obtain three First silicon substrate epoxidation of propylene object；
(1.1.2) mixes water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object, under agitation heating water bath to 84 DEG C, insulation reaction 12min is cooled to room temperature after reaction, and neutralized, distillation, separation and purification are obtained as shown in formula (I) Dihydric alcohol with trimethylsilyl side group, the R in formula (I) are-CH (CH3)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, instead When should start, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:30, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality 0.14%；
(1.2) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and the band for being 1:1.5:0.04:0.026 by molar ratio The dihydric alcohol of trimethylsilyl side group is made into slurry, antimony acetate, titanium dioxide and Trimethyl phosphite is added after mixing, in nitrogen Atmosphere encloses middle pressurization and carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 95% of theoretical value, antimony acetate, titanium dioxide and Trimethyl phosphite plus Enter 0.05wt%, 0.20wt% and 0.05wt% that amount is respectively terephthalic acid (TPA) additional amount；
(1.3) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 42min The interior absolute pressure that is steadily evacuated to by normal pressure is 470Pa, and reaction temperature is 255 DEG C, reaction time 36min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 92Pa, reaction temperature 274 DEG C, reaction time 70min, the number-average molecular weight of modified poly ester obtained is 26300, molecular weight distributing index 2.4；
(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.2dL/g, the polyester tow that it is 3.3% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 232 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.6m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 8.5mm, and the spacing between last group of setting roller and take-up roll is 368mm, the spacing between two hot plates and last group of setting roller are 260mm；
Spinning technology parameter is as follows: each area's temperature of screw rod is 310 DEG C；Spin manifold temperature is 300 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 80%；Cross air blasting wind speed is 0.6m/s；Winding speed is 2650m/ min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 500m/min；One roll temperature is 26 DEG C；Two roller speeds are 800m/ min；Two roll temperatures are 90 DEG C；Three roller speeds are 2200m/min；Three roll temperatures are 120 DEG C；Four roller speeds are 3200m/min；Four Roll temperature is 220 DEG C；Five roller speeds are 3200m/min；Five roll temperatures are 230 DEG C；Six roller speeds are 2740m/min；Six roller temperatures Degree is 200 DEG C；
The filament number of modified polyester industrial yarns is 4.0dtex, breaking strength 7.9cN/dtex, and line density deviation ratio is 1.4%, breaking strength CV value be 2.8%, elongation at break 19.0%, extension at break CV value be 7.4%, 190 DEG C × Dry-hot shrinkage under the conditions of 15min × 0.01cN/dtex is 2.8%, and internet pricing is 5/m, LOI 32；
(3) modified polyester industrial yarns are weaved into Cheng Buhou in the surface calender lamination PVC of modified polyester industrial yarns woven cloths The terylene fire retardant canvas that fabric construction is 1/1 plain weave is made in film, weaves and the technological parameter of primary coat is the same as embodiment 2, calender lamination Temperature be 170 DEG C, pressure 5.2MPa, time 80s；PVC film is located at the double-sided surface of modified polyester industrial yarns woven cloths, Unilateral PVC film with a thickness of 0.65mm.
Terylene fire retardant canvas has lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer, The grammes per square metre of terylene fire retardant canvas is 700g/m2, flaming combustion time 1.5s, glowing time 2.3s, adhesive strength is 55N/cm, peel strength 8.3N/cm, longitudinal tensile strength 287N/cm, transverse tensile strength 290N/cm, longitudinal fracture Elongation is 6.3%, and transverse breakage elongation is 5.6%, and use temperature range is -30 DEG C~+50 DEG C, and resistance to hydrostatic pressure value is 95KPa, resistance to hydrostatic pressure value are fabric under the hydraulic pressure effect of lasting rising, and pressure value when infiltration, rub resistance has just taken place Secondary numerical value is 3200 times, and rub resistance time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.
Embodiment 6
The preparation method of terylene fire retardant canvas, steps are as follows:
(1) modified poly ester is prepared；
(1.1) dihydric alcohol with trimethylsilyl side group is prepared；
(1.1.2) is mixed 3- trimethylsilyl -3,3- dimethyl allene, peracetic acid and methylene chloride by the molar ratio of 1:8:12 Close, react 5h under the conditions of 40 DEG C of temperature, when reaction, accompanies by stirring, removes solvent after reaction, it is purified be refining to obtain To trimethylsilyl epoxidation of propylene object；
(1.1.2) mixes water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object, under agitation heating water bath to 85 DEG C, insulation reaction 10min is cooled to room temperature after reaction, and neutralized, distillation, separation and purification are obtained as shown in formula (I) Dihydric alcohol with trimethylsilyl side group, the R in formula (I) are-C ((CH3)2)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, instead When should start, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:25, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality 0.12%；
(1.2) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and the band for being 1:1.6:0.042:0.027 by molar ratio The dihydric alcohol of trimethylsilyl side group is made into slurry, antimony acetate, titanium dioxide and trimethyl phosphate is added after mixing, in nitrogen Pressurization carries out esterification in atmosphere, and moulding pressure 0.3MPa, the temperature of esterification is 255 DEG C, when in esterification Water quantity of distillate is esterification terminal, the additional amount of antimony acetate, titanium dioxide and trimethyl phosphate when reaching the 95% of theoretical value Respectively 0.03~the wt%, 0.20wt% and 0.01wt% of terephthalic acid (TPA) additional amount；
(1.3) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 46min The interior absolute pressure that is steadily evacuated to by normal pressure is 500Pa, and reaction temperature is 258 DEG C, reaction time 38min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 95Pa, reaction temperature 275 DEG C, reaction time 80min, the number-average molecular weight of modified poly ester obtained is 26700, molecular weight distributing index 2.1；
(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.2dL/g, the polyester tow that it is 3.2% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 235 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 3.8m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 9mm, and the spacing between last group of setting roller and take-up roll is 384mm, the spacing between two hot plates and last group of setting roller are 280mm；
Spinning technology parameter is as follows: each area's temperature of screw rod is 310 DEG C；Spin manifold temperature is 300 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 80%；Cross air blasting wind speed is 0.6m/s；Winding speed is 3330m/ min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 500m/min；One roll temperature is 26 DEG C；Two roller speeds are 800m/ min；Two roll temperatures are 90 DEG C；Three roller speeds are 2200m/min；Three roll temperatures are 120 DEG C；Four roller speeds are 3200m/min；Four Roll temperature is 220 DEG C；Five roller speeds are 3200m/min；Five roll temperatures are 230 DEG C；Six roller speeds are 3440m/min；Six roller temperatures Degree is 200 DEG C；
The filament number of modified polyester industrial yarns is 4.0dtex, breaking strength 7.8cN/dtex, and line density deviation ratio is 1.4%, breaking strength CV value be 2.8%, elongation at break 20.0%, extension at break CV value be 7.4%, 190 DEG C × Dry-hot shrinkage under the conditions of 15min × 0.01cN/dtex is 2.9%, and internet pricing is 5/m, LOI 33；
(3) modified polyester industrial yarns are weaved into Cheng Buhou in the surface calender lamination PVC of modified polyester industrial yarns woven cloths The terylene fire retardant canvas that fabric construction is 1/1 plain weave is made in film, weaves and the technological parameter of primary coat is the same as embodiment 1, calender lamination Temperature be 170 DEG C, pressure 5.2MPa, time 80s；PVC film is located at the double-sided surface of modified polyester industrial yarns woven cloths, Unilateral PVC film with a thickness of 0.65mm.
Terylene fire retardant canvas has lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer, The grammes per square metre of terylene fire retardant canvas is 700g/m2, flaming combustion time 1.5s, glowing time 2.3s, adhesive strength is 56N/cm, peel strength 8.5N/cm, longitudinal tensile strength 287N/cm, transverse tensile strength 295N/cm, longitudinal fracture Elongation is 6.3%, and transverse breakage elongation is 5.6%, and use temperature range is -30 DEG C~+50 DEG C, and resistance to hydrostatic pressure value is 96KPa, resistance to hydrostatic pressure value are fabric under the hydraulic pressure effect of lasting rising, and pressure value when infiltration, rub resistance has just taken place Secondary numerical value is 3200 times, and rub resistance time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.
Embodiment 7
The preparation method of terylene fire retardant canvas, steps are as follows:
(1) modified poly ester is prepared；
(1.1) dihydric alcohol with trimethylsilyl side group is prepared；
(1.1.1) is by the molar ratio of 1:10:10 by 3- trimethylsilyl -3,3- dimethyl allene, peracetic acid and methylene chloride Mixing, reacts 6h under the conditions of 35 DEG C of temperature, and when reaction accompanies by stirring, removes solvent after reaction, purified and refine Obtain trimethylsilyl epoxidation of propylene object；
(1.1.2) mixes water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object, under agitation heating water bath to 80 DEG C, insulation reaction 15min is cooled to room temperature after reaction, and neutralized, distillation, separation and purification are obtained as shown in formula (I) Dihydric alcohol with trimethylsilyl side group, the R in formula (I) are-C ((CH3)2)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, instead When should start, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:35, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality 0.14%；
(1.2) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and the band for being 1:1.7:0.043:0.028 by molar ratio The dihydric alcohol of trimethylsilyl side group is made into slurry, antimony glycol, titanium dioxide and trimethyl phosphate is added after mixing, in nitrogen Atmosphere encloses middle pressurization and carries out esterification, and moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when in esterification Water quantity of distillate be esterification terminal when reaching the 95% of theoretical value, antimony glycol, titanium dioxide and trimethyl phosphate plus Enter 0.05wt%, 0.25wt% and 0.01wt% that amount is respectively terephthalic acid (TPA) additional amount；
(1.3) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 35min The interior absolute pressure that is steadily evacuated to by normal pressure is 490Pa, and reaction temperature is 259 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 83Pa, reaction temperature 282 DEG C, reaction time 85min, the number-average molecular weight of modified poly ester obtained is 27000, molecular weight distributing index 1.9；
(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.2dL/g, the polyester tow that it is 3.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 240 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 4.0m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 10mm, and the spacing between last group of setting roller and take-up roll is 400mm, the spacing between two hot plates and last group of setting roller are 300mm；
Spinning technology parameter is as follows: each area's temperature of screw rod is 320 DEG C；Spin manifold temperature is 300 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 85%；Cross air blasting wind speed is 0.7m/s；Winding speed is 2658m/ min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 600m/min；One roll temperature is 26 DEG C；Two roller speeds are 1000m/min；Two roll temperatures are 100 DEG C；Three roller speeds are 2500m/min；Three roll temperatures are 150 DEG C；Four roller speeds are 3500m/min；Four roll temperatures are 250 DEG C；Five roller speeds are 3500m/min；Five roll temperatures are 250 DEG C；Six roller speeds are 2740m/min；Six roll temperatures are 220 DEG C；
The filament number of modified polyester industrial yarns is 5.0dtex, breaking strength 7.7cN/dtex, and line density deviation ratio is 1.5%, breaking strength CV value be 2.9%, elongation at break 20.0%, extension at break CV value be 7.4%, 190 DEG C × Dry-hot shrinkage under the conditions of 15min × 0.01cN/dtex is 3.1%, and internet pricing is 8/m, LOI 33；
(2) modified polyester industrial yarns are weaved into Cheng Buhou in the surface calender lamination PVC of modified polyester industrial yarns woven cloths The terylene fire retardant canvas that fabric construction is 1/1 plain weave is made in film, weaves and the technological parameter of primary coat is the same as embodiment 3, calender lamination Temperature be 170 DEG C, pressure 5.5MPa, time 90s；PVC film is located at the double-sided surface of modified polyester industrial yarns woven cloths, Unilateral PVC film with a thickness of 0.75mm.
Terylene fire retardant canvas has lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer, The grammes per square metre of terylene fire retardant canvas is 800g/m2, flaming combustion time 1.5s, glowing time 2.5s, adhesive strength is 58N/cm, peel strength 8.7N/cm, longitudinal tensile strength 290N/cm, transverse tensile strength 300N/cm, longitudinal fracture Elongation is 6.4%, and transverse breakage elongation is 5.6%, and use temperature range is -30 DEG C~+60 DEG C, and resistance to hydrostatic pressure value is 96KPa, resistance to hydrostatic pressure value are fabric under the hydraulic pressure effect of lasting rising, and pressure value when infiltration, rub resistance has just taken place Secondary numerical value is 3300 times, and rub resistance time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.
Embodiment 8
The preparation method of terylene fire retardant canvas, steps are as follows:
(1) modified poly ester is prepared；
(1.1) dihydric alcohol with trimethylsilyl side group is prepared；
(1.1.1) is mixed 3- trimethylsilyl -3,3- dimethyl allene, peracetic acid and methylene chloride by the molar ratio of 1:5:15 Close, react 7h under the conditions of 37 DEG C of temperature, when reaction, accompanies by stirring, removes solvent after reaction, it is purified be refining to obtain To trimethylsilyl epoxidation of propylene object；
(1.1.2) mixes water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object, under agitation heating water bath to 82 DEG C, insulation reaction 12min is cooled to room temperature after reaction, and neutralized, distillation, separation and purification are obtained as shown in formula (I) Dihydric alcohol with trimethylsilyl side group, the R in formula (I) are-C ((CH3)2)-, the concentrated sulfuric acid is the sulfuric acid that mass concentration is 70%, instead When should start, the molar ratio of trimethylsilyl epoxidation of propylene object and water is 1:29, and the quality of the concentrated sulfuric acid accounts for the sum of mixture quality 0.13%；
(1.2) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and the band three for being 1:1.7:0.05:0.03 by molar ratio The dihydric alcohol of first silicon substrate side group is made into slurry, antimony glycol, titanium dioxide and triphenyl phosphate is added after mixing, in nitrogen Pressurization carries out esterification in atmosphere, and moulding pressure 0.3MPa, the temperature of esterification is 260 DEG C, when in esterification Water quantity of distillate is esterification terminal, the addition of antimony glycol, titanium dioxide and triphenyl phosphate when reaching the 95% of theoretical value Amount is respectively 0.05wt%, 0.25wt% and 0.05wt% of terephthalic acid (TPA) additional amount；
(1.3) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 50min The interior absolute pressure that is steadily evacuated to by normal pressure is 400Pa, and reaction temperature is 260 DEG C, reaction time 50min, then proceedes to take out true Sky carries out the polycondensation reaction of high vacuum stage of Fig, and reaction pressure is made to be further reduced to absolute pressure 96Pa, reaction temperature 274 DEG C, reaction time 90min, the number-average molecular weight of modified poly ester obtained is 28000, molecular weight distributing index 2.4；
(2) by modified poly ester melt carry out solid phase polycondensation thickening, melting, metering, extrusion, cooling, oil, stretch, heat it is fixed Modified polyester industrial yarns are made in type, heat treatment without tension and winding, and wherein the inherent viscosity of modified poly ester is after solid phase polycondensation thickening 1.2dL/g, the polyester tow that it is 3.0% by the over feed rate(OFR) of winding that heat treatment without tension, which refers to, is by a pair of arranged in parallel and non-co-planar Temperature is the space between 240 DEG C of hot plate simultaneously, hot plate be located in FDY equipment last group of setting roller and take-up roll it Between, along the traffic direction of polyester tow, the length of two hot plates is 4.0m, and the both ends of two hot plates flush, and polyester tow is from two hot plates When centre passes through, the distance between two hot plates are 10mm, and the spacing between last group of setting roller and take-up roll is 400mm, the spacing between two hot plates and last group of setting roller are 300mm；
Spinning technology parameter is as follows: each area's temperature of screw rod is 320 DEG C；Spin manifold temperature is 300 DEG C；Head pressure is 140bar；Side-blown air temperature is 22 DEG C；Side-blown wind moisture is 85%；Cross air blasting wind speed is 0.7m/s；Winding speed is 2658m/ min；It stretches, the technological parameter of thermal finalization are as follows: a roller speed is 600m/min；One roll temperature is 26 DEG C；Two roller speeds are 1000m/min；Two roll temperatures are 100 DEG C；Three roller speeds are 2500m/min；Three roll temperatures are 150 DEG C；Four roller speeds are 3500m/min；Four roll temperatures are 250 DEG C；Five roller speeds are 3500m/min；Five roll temperatures are 250 DEG C；Six roller speeds are 2740m/min；Six roll temperatures are 220 DEG C；
The filament number of modified polyester industrial yarns is 5.0dtex, breaking strength 7.5cN/dtex, line density deviation ratio It is -1.5%, breaking strength CV value is 3.0%, elongation at break 18.0%, and extension at break CV value is≤8.0%, at 190 DEG C Dry-hot shrinkage under the conditions of × 15min × 0.01cN/dtex is 3.3%, and internet pricing is 10/m, LOI 34；
(2) modified polyester industrial yarns are weaved into Cheng Buhou in the surface calender lamination PVC of modified polyester industrial yarns woven cloths The terylene fire retardant canvas that fabric construction is 1/1 plain weave is made in film, weaves and the technological parameter of primary coat is the same as embodiment 1, calender lamination Temperature be 170 DEG C, pressure 5.5MPa, time 90s；PVC film is located at the double-sided surface of modified polyester industrial yarns woven cloths, Unilateral PVC film with a thickness of 0.75mm.
Terylene fire retardant canvas has lamination layer structure, is mainly made of modified polyester industrial yarns woven layer and PVC film layer, The grammes per square metre of terylene fire retardant canvas is 800g/m2, flaming combustion time 1.5s, glowing time 2.5s, adhesive strength is 60N/cm, peel strength 8.8N/cm, longitudinal tensile strength 290N/cm, transverse tensile strength 300N/cm, longitudinal fracture Elongation is 6.5%, and transverse breakage elongation is 6.0%, and use temperature range is -30 DEG C~+60 DEG C, and resistance to hydrostatic pressure value is 97KPa, resistance to hydrostatic pressure value are fabric under the hydraulic pressure effect of lasting rising, and pressure value when infiltration, rub resistance has just taken place Secondary numerical value is 3300 times, and rub resistance time numerical value is fabric under continuous frictional effect, and Rubbing number when variation has just taken place.

Claims (10)

1. the preparation method of terylene fire retardant canvas, it is characterized in that: in the surface calender lamination PVC of modified polyester industrial yarns woven cloths Terylene fire retardant canvas is made in film；
The modified polyester industrial yarns are by the way that modified poly ester melt is carried out solid phase polycondensation thickening, melting, metering, extrusion, cold But, oil, stretch, made from thermal finalization, heat treatment without tension and winding；
Modified poly ester the preparation method comprises the following steps: by terephthalic acid (TPA), ethylene glycol, band trimethylsilyl side group before the solid phase polycondensation viscosifies Dihydric alcohol and 2- carboxyethyl phenyl hypophosphorous acid successively carry out esterification and polycondensation reaction after mixing；
The structural formula of dihydric alcohol with trimethylsilyl side group is as follows:
In formula, R is-CH2-、-CH(CH3)-or-C ((CH3)2)-；
The heat treatment without tension refers to the space by modified poly ester tow in relaxed state appropriate Jing Guo certain temperature；
The relaxed state appropriate refers to that the over feed rate(OFR) of winding is 3.0~5.0%；
The certain temperature refers to 200~240 DEG C.
2. the preparation method of terylene fire retardant canvas according to claim 1, which is characterized in that the band trimethylsilyl side group Dihydric alcohol synthesis step it is as follows:
(1) raw material alkene, peracetic acid and methylene chloride are mixed by the molar ratio of 1:5~10:10~15, in 35~40 DEG C of temperature Under the conditions of react 5~8h, when reaction, accompanies by stirring, removes solvent after reaction, it is purified be refining to obtain trimethylsilyl third Alkene epoxides；
(2) water, the concentrated sulfuric acid and trimethylsilyl epoxidation of propylene object mixing, heating water bath is to 80~85 DEG C under agitation, Insulation reaction l0~15min, is cooled to room temperature after reaction, and neutralized, distillation, separation and purification obtain band trimethylsilyl side The dihydric alcohol of base, the concentrated sulfuric acid is the sulfuric acid of mass concentration 70%, when reaction starts, trimethylsilyl epoxidation of propylene object and water Molar ratio be 1:20~40, the quality of the concentrated sulfuric acid accounts for the 0.1~0.15% of the sum of mixture quality；
R is-CH (CH in the structural formula of the dihydric alcohol with trimethylsilyl side group3)-and-C ((CH3)2)-when, the raw material alkene Correspond to 3- trimethylsilyl -3- metering system and 3- trimethylsilyl -3,3- dimethyl allene.
3. the preparation method of terylene fire retardant canvas according to claim 2, which is characterized in that before the solid phase polycondensation thickening The preparation step of modified poly ester is as follows:
(1) esterification；
Terephthalic acid (TPA), ethylene glycol, 2- carboxyethyl phenyl hypophosphorous acid and dihydric alcohol with trimethylsilyl side group are made into slurry, added Enter catalyst, delustering agent and stabilizer after mixing, pressurization carries out esterification in nitrogen atmosphere, and moulding pressure is normal pressure ~0.3MPa, the temperature of esterification are 250~260 DEG C, when the water quantity of distillate in esterification reach the 90% of theoretical value with It was esterification terminal when upper；
(2) polycondensation reaction；
After esterification, start the polycondensation reaction of low vacuum stage under condition of negative pressure, the staged pressure is in 30~50min Interior to be steadily evacuated to absolute pressure 500Pa hereinafter, reaction temperature is 250~260 DEG C by normal pressure, the reaction time is 30~50min, so After continue to vacuumize, carry out the polycondensation reaction of high vacuum stage of Fig, so that reaction pressure is further reduced to absolute pressure 100Pa hereinafter, Reaction temperature is 270~282 DEG C, and the reaction time is 50~90min.
4. the preparation method of terylene fire retardant canvas according to claim 3, which is characterized in that the terephthalic acid (TPA), second The molar ratio of glycol, 2- carboxyethyl phenyl hypophosphorous acid and the dihydric alcohol with trimethylsilyl side group be 1:1.2~2.0:0.03~ 0.05:0.02~0.03, the additional amount of the catalyst, delustering agent and stabilizer are respectively the 0.03 of terephthalic acid (TPA) additional amount ~0.05wt%, 0.20~0.25wt% and 0.01~0.05wt%.
5. the preparation method of terylene fire retardant canvas according to claim 4, which is characterized in that the catalyst is three oxidations Two antimony, antimony glycol or antimony acetate, the delustering agent are titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate Or Trimethyl phosphite.
6. the preparation method of terylene fire retardant canvas according to claim 5, which is characterized in that after the solid phase polycondensation thickening The inherent viscosity of modified poly ester is 1.0~1.2dL/g.
7. the preparation method of terylene fire retardant canvas according to claim 1, which is characterized in that the space of the certain temperature Refer to the space between a pair of arranged in parallel and non-coplanar hot plate, hot plate be located in FDY equipment last group of setting roller and Between take-up roll；Along the traffic direction of modified poly ester tow, the length of two hot plates is 3.0~4.0m, and the both ends of two hot plates flush； When modified poly ester tow passes through among two hot plates, the distance between two hot plates are 5~10mm；
Spacing between last group of setting roller and take-up roll is 300~400mm；Two hot plates and last group of setting roller it Between spacing be 200~300mm.
8. the preparation method of terylene fire retardant canvas according to claim 1, which is characterized in that the modified polyester industrial yarns Spinning technology parameter it is as follows:
It stretches, the technological parameter of thermal finalization are as follows:
The temperature of the calender lamination is 165~170 DEG C, and pressure is 5~5.5MPa, and the time is 75~90s；The PVC film position In the double-sided surface of modified polyester industrial yarns woven cloths, unilateral PVC film with a thickness of 0.40~0.75mm.
9. using terylene fire retardant canvas made from the preparation method of terylene fire retardant canvas as described in any one of claim 1~8, It is characterized in: there is lamination layer structure, be mainly made of modified polyester industrial yarns woven layer and PVC film layer；
The strand of the modified poly ester includes terephthalic acid (TPA) segment, ethylene glycol segment, 2- carboxyethyl phenyl hypophosphorous acid and band The dihydric alcohol segment of trimethylsilyl side group.
10. terylene fire retardant canvas according to claim 9, which is characterized in that the filament number of modified polyester industrial yarns is 3.0~5.0dtex, breaking strength >=7.5cN/dtex, line density deviation ratio are ± 1.5%, breaking strength CV value≤3.0%, Elongation at break is 18.0~20.0%, extension at break CV value≤8.0%, in 190 DEG C × 15min × 0.01cN/dtex condition Under dry-hot shrinkage be 2.5~3.3%, internet pricing be (5~8) ± 2/m, LOI be 30~34；
The grammes per square metre of terylene fire retardant canvas is 500~800g/m2, flaming combustion time is less than or equal to 1.5s, and glowing time is less than Equal to 2.5s, adhesive strength is 50~60N/cm, peel strength >=8.5N/cm, and longitudinal tensile strength is more than or equal to 281N/cm, Transverse tensile strength be more than or equal to 285N/cm, longitudinal elongation at break rate be 6.3~6.5%, transverse breakage elongation be 5.6~ 6.0%, use temperature range is -30 DEG C~+60 DEG C, resistance to hydrostatic pressure value >=90KPa, and resistance to hydrostatic pressure value is fabric in lasting rising Hydraulic pressure effect under, just taken place pressure value when infiltration, rub resistance time numerical value >=3000 time, rub resistance time numerical value is fabric Under continuous frictional effect, Rubbing number when variation has just taken place.
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