CN101407577A - Low-melting point phosphor-containing flame-retardant copolyester and preparation thereof - Google Patents
Low-melting point phosphor-containing flame-retardant copolyester and preparation thereof Download PDFInfo
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Abstract
The invention disclose a low-melting-point phosphoric inflaming retarding copolyesters which are produced by basic composite polyester constitutional units expressed by I and II and introduced constitutional units expressed by III and IV, through random copolymerization; wherein, the number of III constitutional units is about 1 to 80 percent of the number of I constitutional units, and the number of IV constitutional units is about 1 to 15 percent of the number of I constitutional units. The number of (I+IV) constitutional units to the number of (II + III) constitutional units is equal to one; intrinsic viscosity number of prepared low-melting-point inflaming retarding copolyesters is 0.40 to 0.99dL/g; the melting point is 100 to 220 DEG C; oxygen index is 28 to 49 percent; and the vertical burn degree is V-0. The invention also discloses a preparing method thereof. Owing to the introduction of constitutional units expressed by IV as phosphoric inflaming retarding monomer, the effect of modifying inflaming retarding characteristics and lowering melting points of polyester is realized. The copolyesters is characterized by good fiberizability, therefore the fibers of the copolyesters can be widely applied to textile and non-woven fabric industries, and aslo can be directly applied in industries such as building materials, paint, etc.
Description
Technical field
The invention belongs to copolyester with low melting point and preparation method thereof technical field.Be specifically related to a kind of phosphorous copolyester that has low melting point and flame retardant properties simultaneously and preparation method thereof.
Background technology
In the synthon of one of three big synthesized polymer materials, polyester (specially refers to polyethylene terephthalate here, PET) because have advantages such as high-modulus, high strength, snappiness, conformality and thermotolerance, make it just become output maximum in the synthon, the fiber species that purposes is the widest in 1972.But, two of polyester big main raw material terephthalic acids (TPA) and ethylene glycol (EG) are appreciated by crude oil in recent years influences, price rises steadily, increased the production cost of enterprise, domestic many production of polyester scopes of the enterprise are less relatively simultaneously, and production technology is comparatively backward, and outlet is obstructed in addition, thereby cause domestic polyester supply to increase suddenly, the market competition aggravation.Particularly the polyester overwhelming majority of China is as fiber usefulness, and mainly is as the normal polyester fiber, and this kind polyester significantly glides enterprise profit because of being in the situation that supply exceed demand, in addition in having much, small-scale enterprise production line stops production.Thereby research and development functionalized polyester product innovation is one of approach that changes this predicament.
Low-melting point polyester is a kind of functionalized polyester product innovation of developing in the last few years, and it is the atactic polyester of introducing flexible group or preparing with many monomer copolymerizations by in the polyester synthesis technique.Because the introducing of flexible group or the regularity and the symmetry of polyester molecule chain that adopted many monomer copolymerizations partial destruction, thereby the fusing point of reduction polyester, thereby obtained low-melting point polyester (Cheng Zhenjuan, Luo Hailin, Qian Jianhua, Sun Fu. the Application and Development of low-melting point polyester. Jinan textile chemical fiber science and technology .2007,2:19-21; Tang poetry, Yao Jianbo, Li Yanli. the synthetic and performance study of low-melting point polyester. Beijing Institute of Clothing Tech's journal, 2002,22:8-10; Lin Shengbing, Yao Feng, Qu Zhongkai, Guo Yonglin, Jin Yonglong. the synthetic and performance study of low-melting point polyester. synthetic fiber industry, 2005,28:13-16.).Low-melting point polyester also is used for the manufacturing of non-woven except being used for polyester hot-melt adhesive and core-skin composite fiber, as being mixed together the back as the heat-bondable fibre of making in the non-woven with the normal polyester fiber.When manufacturing non-woven, both can be used for high-grade clothing and pasted arm of angle lining, can be used for fields such as automotive industry, construction industry, civil engineering work, house decoration decoration, health care and agricultural again.But, because problems such as polyester inherent inflammableness and fusion drippage property, make at some key areas, application as the textiles in electron device, fire retardant protective clothing and military uniform, the vehicles, hotel furnishing fabric etc. is restricted, and is particularly increased severely people to be craved for use and is had excellent performance low melting point flame retardance poly ester material by the catch fire loss that particularly serious fire caused that causes of macromolecular material in recent years.
Though the research and development to fire-retardant polyester fibre have just begun to enliven since the seventies, various fire-retardant polyester fibres constantly come out, and yet there are no at present the correlative study report aspect fire-retardant in the low-melting point polyester product.
Summary of the invention
The objective of the invention is at the present problem that exists of low-melting point polyester, a kind of low-melting point phosphor-containing flame-retardant copolyester is provided, this low melting point flame-proof copolyester Halogen, nontoxic not only can also can directly apply to industries such as building materials, coating directly as the fiber flame-proof copolyester.
Two of purpose of the present invention provides the preparation method of above-mentioned phosphorous low melting point flame-proof copolyester.
Low-melting point phosphor-containing flame-retardant copolyester provided by the invention, this flame-proof copolyester is made up of the structural unit that following I, II, III and IV represent:
In the formula, R
1The expression arylidene, R
2Expression C
3～C
8The straight or branched alkyl, R
3Be C
1～C
12Straight or branched alkyl, aryl or benzyl, R
4Be C
1～C
8Straight or branched alkylidene group, aryl or fatty aryl radical, X, Y represent O or S atom,
Wherein the structural unit number of III be I the structural unit number 1～80%, preferred 2～75%, the structural unit number of IV be I the structural unit number 1～15%, preferred 1～10%, the structural unit number of [I+IV]: structural unit number=1 of [II+III], the segment of each structural unit or its formation is to be connected combination by carboxyl arbitrarily with hydroxy functional group, and the intrinsic viscosity of this flame-proof copolyester [η] is 0.55～0.90dL/g, fusing point is 100-220 ℃, oxygen index is 28-48%, and the vertical combustion grade is V-0.
The method of the above-described low-melting point phosphor-containing flame-retardant copolyester of preparation provided by the invention, this method is with terephthalic acid or its carboxylate and ethylene glycol, catalyzer proportioning routinely, after adopting direct esterification method or ester-interchange method to carry out esterification, be prepared from through polycondensation, it is characterized in that before esterification or the esterification aftercondensated before, in reaction system, add and count 1～80% the 3rd monomer by the molecular fraction of diprotic acid or its carboxylate, preferred 2～75%, with 1～15% the 4th monomer, preferred 1～10%.Wherein the 3rd monomeric general structure is as follows:
HO-R
2·OH
In the formula, R
2Be C
3～C
8The straight or branched alkyl.
The 4th monomer is a response type phosphor-containing flame-proof monomer.Be specially compound with following general structure:
In the formula, R
3Be C
1～C
12Straight or branched alkyl, aryl or benzyl, R
4Be C
1～C
8Straight or branched alkylidene group, aryl or fatty aryl radical, X represents O or S atom.
Perhaps for having 9 of following general structure, the 10-dihydro-9-oxy is mixed-the assorted luxuriant and rich with fragrance compounds of 10-phosphono:
In the formula, Y represents O or S atom, Z
1, Z
2Be hydroxy-acid group or ester group group, Z
1, Z
2Identical or inequality.
Response type phosphor-containing flame-proof monomer 9, the 10-dihydro-9-oxy is assorted-the assorted luxuriant and rich with fragrance compounds of 10-phosphono in the ester group group be the methyl esters group after the monohydroxy-alcohol esterification or be the glycol ester group behind the dibasic alcohol ester.
The processing step and the condition of conventional direct esterification method of the present invention or ester-interchange method are as follows:
The direct esterification method: add polyester monocase, catalyzer and response type phosphor-containing flame-proof monomer by proportioning in reactor, pressurization is warmed up to 220～260 ℃ and carried out esterification 2～6 hours; After esterification finishes, under the rough vacuum in 260～280 ℃ of polycondensations 0.5～1.5 hour, then under high vacuum in 275～285 ℃ of polycondensations 1～3 hour, extrude the copolyesters melt with nitrogen, water-cooled, low-melting point phosphor-containing flame-retardant copolyester.Wherein, the 3rd monomer can be chosen in before the esterification or add reactor before the esterification aftercondensated.
Ester-interchange method: add polyester monocase, catalyzer and response type phosphor-containing flame-proof monomer by proportioning in reactor, normal pressure carried out transesterification reaction 3～5 hours in 185～275 ℃; After transesterify finishes, under the rough vacuum in 260～280 ℃ of polycondensations 0.5～1.5 hour, then under high vacuum in 275～285 ℃ of polycondensations 1～3 hour, extrude the copolyesters melt with nitrogen, water-cooled, low-melting point phosphor-containing flame-retardant copolyester.Wherein, the 3rd monomer can be chosen in before the transesterify or add reactor before the transesterify aftercondensated.
Selected catalyzer is the mixture of any one or they in manganese acetate, zinc acetate, Cobaltous diacetate, antimonous oxide, antimony glycol, the titanic acid ester in the inventive method.
The present invention has the following advantages:
1, owing to existing flexible unit in the structural unit of low-melting point phosphor-containing flame-retardant copolyester provided by the invention, the fire-retardant unit of phosphorated is arranged again, and the fire-retardant unit of phosphorated can not only play fire-retardant effect, can also play the regularity and the symmetric effect that destroy the polyester molecule chain, thereby the not only collaborative fusing point that has reduced polyester, also give the polyester flame-retardant performance simultaneously, realized the multifunction modification of low-melting point polyester.
2, because the fire-retardant unit in the structural unit of low-melting point phosphor-containing flame-retardant copolyester provided by the invention is to belong to the response type P contained compound, thereby it is poor not only can to avoid additive flame retardant to exist with the consistency of polyester matrix, spinning property is bad, and problem such as durability of fire-retardant difference, also make this copolyesters have characteristics such as Halogen, nontoxic, low melting point, high flame retardant, environmental protection.
3, phosphorous low melting point flame-proof copolyester provided by the invention not only can be directly as the fiber flame-proof copolyester, the part characteristic that has also kept polyester because of it, with conventional polyester good consistency is arranged, its fiber also can be widely used in weaving, non-woven fabrics industry, also can directly apply to industries such as building materials, coating simultaneously.
4, preparation method's maturation provided by the invention is simple and convenient, is easy to control and suitability for industrialized production.
Embodiment
Provide embodiment below so that the invention will be further described.Be necessary to be pointed out that at this following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
In addition, intrinsic viscosity [η] that what deserves to be explained is following examples products therefrom all be with phenol/sym.-tetrachloroethane (1: 1, v: be solvent v), be mixed with the solution that concentration is 0.5g/dL, record at 25 ℃ with dark type viscometer; Limiting oxygen index(LOI) all is to be made into 120 * 6.5 * 3.2mm
3The standard oxygen exponential spline, on the HC-2C oxygen index instrument, measure; Vertical combustion then is to be made into 125 * 12.7 * 3.2mm
3The standard batten, adopt CZF-2 type vertical combustion instrument to measure; Fusing point is that the DSC Q200 of TA company measures.
Embodiment 1
860g terephthalic acid, 483g ethylene glycol, 20.8g the 3rd monomer neopentyl glycol (NPG), 31.1g the 4th monomer 2-carboxyethyl phenyl phosphinic acid (HPPPA) and 0.301g antimonous oxide are joined in the reactor, inflated with nitrogen is got rid of air in the kettle, be pressurized to 0.07Mpa, and in 2h, be warming up to 240 ℃, in the still internal pressure is 0.3～0.4MPa, esterification 2h; Step-down also rises to 260 ℃ with temperature gradually behind 1.5h, pressure is reduced to normal pressure, and esterification finishes.Then at 260～270 ℃ of rough vacuum polycondensation 0.5h, (polycondensation of pressure＜60Pa) is after 1～3 hour, discharging to be warming up to 275～285 ℃ of high vacuum subsequently.
The intrinsic viscosity of this copolyesters [η] is 0.70dL/g, and oxygen index is 30.2%, and vertical combustion grade V-0, fusing point are 219.8 ℃.
Embodiment 2
860g terephthalic acid, 432g ethylene glycol, 107.4gNPG, 32.2gHPPPA and 0.301g antimonous oxide are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.69dL/g, and oxygen index is 33.9%, and vertical combustion grade V-0, fusing point are 210.9 ℃.
Embodiment 3
860g terephthalic acid, 425.6g ethylene glycol, 137.3gNPG, 55.4gHPPPA and 0.301g antimonous oxide are joined in the reactor, inflated with nitrogen is got rid of air in the kettle, is pressurized to 0.07Mpa, and is warming up to 240 ℃ in 2h, in the still internal pressure is 0.3～0.4MPa, esterification 2h; Step-down also rises to 260 ℃ with temperature gradually behind 1.5h, pressure is reduced to normal pressure, and esterification finishes.Then at 260～270 ℃ of rough vacuum polycondensation 0.5h, (polycondensation of pressure＜60Pa) is after 0.5～1.5 hour, discharging to be warming up to 275～285 ℃ of high vacuum subsequently.
The intrinsic viscosity of this copolyesters [η] is 0.41dL/g, and oxygen index is 35.5%, and vertical combustion grade V-0, fusing point are 165.7 ℃.
Embodiment 4
860g terephthalic acid, 492g ethylene glycol, 21.3gNPG, 53.1gHPPPA and 0.301g antimonous oxide are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.71dL/g, and oxygen index is 34.1%, and vertical combustion grade V-0, fusing point are 213.0 ℃.
Embodiment 5
860g terephthalic acid, 473g ethylene glycol, 53.8gNPG, 53.8gHPPPA and 0.301g antimonous oxide are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.74dL/g, and oxygen index is 35.0%, and vertical combustion grade V-0, fusing point are 207.0 ℃.
Embodiment 6
860g terephthalic acid, 440g ethylene glycol, 110.0gNPG, 55.1gHPPPA and 0.301g antimonous oxide are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.73dL/g, and oxygen index is 37.6%, and vertical combustion grade V-0, fusing point are 171.2 ℃.
Embodiment 7
860g terephthalic acid, 362g ethylene glycol, 242.6gNPG, 55.4gHPPPA and 0.301g antimonous oxide are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.74dL/g, and oxygen index is 38.4%, and vertical combustion grade V-0, fusing point are 129.0 ℃.
Embodiment 8
860g terephthalic acid, 398.3g ethylene glycol, 225.2gNPG, 110.9gHPPPA and 0.301g antimonous oxide are joined in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.69dL/g, and oxygen index is 43.6%, and vertical combustion grade V-0, fusing point are 122.1 ℃.
Embodiment 9
With the 860g terephthalic acid, 424g ethylene glycol, 197.7gNPG, 160.8gHPPPA and 0.301g antimonous oxide join in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.71dL/g, and oxygen index is 47.9%, and vertical combustion grade V-0, fusing point are 116.9 ℃.
Embodiment 10
1000g dimethyl terephthalate (DMT), 639g ethylene glycol, 241.3gNPG, 55.1gHPPPA, 0.25g manganese acetate and 0.35g antimonous oxide are joined in the reactor, inflated with nitrogen is got rid of air in the kettle, normal pressure is warming up to 190 ℃ of transesterification reaction 2h, be warming up to 220 ℃ of reaction 2h again, be warmed up to 270 ℃ of reaction 1h again.After transesterify finished, earlier at 260～270 ℃ of rough vacuum polycondensation 0.5h, (polycondensation of pressure＜60Pa) was after 1.5～4.5 hours, discharging to be warming up to 275～285 ℃ of high vacuum then.
The intrinsic viscosity of this copolyesters [η] is 0.95dL/g, and oxygen index is 38.3%, and vertical combustion grade V-0, fusing point are 129.3 ℃.
Embodiment 11
With 860g terephthalic acid, 388.7g ethylene glycol, 55.4gHPPPA, join in the reactor, inflated with nitrogen is got rid of air in the kettle, be pressurized to 0.07Mpa, and in 2h, be warming up to 240 ℃, be 0.3～0.4MPa in the still internal pressure, esterification 2h; Step-down also rises to 260 ℃ with temperature gradually behind 1.5h, pressure is reduced to normal pressure, and esterification finishes.Cool to 220 ℃, under nitrogen protection, with 214g 1, the 6-hexylene glycol, 0.25g manganese acetate and 0.35g antimonous oxide join in the reactor, at 220 ℃ of reaction 2h, are warmed up to 270 ℃ of reaction 1h again.Again at 260～270 ℃ of rough vacuum polycondensation 0.5h, (polycondensation of pressure＜60Pa) is after 1～3 hour, discharging to be warming up to 275～285 ℃ of high vacuum then.
The intrinsic viscosity of this copolyesters [η] is 0.88dL/g, and oxygen index is 34.0%, and vertical combustion grade V-0, fusing point are 190.2 ℃.
Embodiment 12
With the 860g terephthalic acid, 362g ethylene glycol, 275.3g the 3rd monomer 1,6-hexylene glycol, 55.4gHPPPA and 0.301g antimonous oxide join in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.83dL/g, and oxygen index is 36.7%, and vertical combustion grade V-0, fusing point are 140.5 ℃.
Embodiment 13
With the 860g terephthalic acid, 248.9g ethylene glycol, 489.1g the 3rd monomer 1,6-hexylene glycol, 55.4gHPPPA and 0.301g antimonous oxide join in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.75dL/g, and oxygen index is 35.3%, and vertical combustion grade V-0, fusing point are 103.1 ℃.
Embodiment 14
With 1000g dimethyl terephthalate (DMT), 361g ethylene glycol, 208.8g the 3rd monomer 1,4-butyleneglycol, 55.4gHPPPA, 0.7g tetrabutyl titanate and 0.35g antimonous oxide join in the reactor, inflated with nitrogen is got rid of air in the kettle, normal pressure is warming up to 190 ℃ of transesterification reaction 2h, be warming up to 220 ℃ of reaction 2h again, be warmed up to 270 ℃ of reaction 1h again.After transesterify finishes, earlier at 260～270 ℃ of rough vacuum polycondensation 0.5h, heat up then, (polycondensation of pressure＜60Pa) is after 1～3 hour, discharging for 275～285 ℃ of high vacuum.
The intrinsic viscosity of this copolyesters [η] is 0.68dL/g, and oxygen index is 34.1%, and vertical combustion grade V-0, fusing point are 176.5 ℃.
Embodiment 15
With the 860g terephthalic acid, 363.5g ethylene glycol, 242.6gNPG, 38.6g the 4th monomer 2-carboxyethyl methylphosphinate phospho acid and 0.301g antimonous oxide join in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.64dL/g, and oxygen index is 30.0%, and vertical combustion grade V-0, fusing point are 113.2 ℃.
Embodiment 16
With 860g terephthalic acid, 362g ethylene glycol, 242.6gNPG, 89.6g the 4th monomer 9, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene-Succinic Acid (DDP) of 10-phosphinylidyne and 0.301g antimonous oxide join in the reactor, carry out esterification by step and condition that embodiment 1 provides, after step that provides by embodiment 1 and condition are carried out polycondensation again, discharging.
The intrinsic viscosity of this copolyesters [η] is 0.67dL/g, and oxygen index is 39.8%, and vertical combustion grade V-0, fusing point are 110.7 ℃.
Claims (6)
1, a kind of low-melting point phosphor-containing flame-retardant copolyester, this flame-proof copolyester is made up of the structural unit that following I, II, III and IV represent:
In the formula, R
1The expression arylidene, R
2Expression C
3～C
8The straight or branched alkyl, R
3Be C
1～C
12Straight or branched alkyl, aryl or benzyl, R
4Be C
1～C
8Straight or branched alkylidene group, aryl or fatty aryl radical, X, Y represent O or S atom,
Wherein the structural unit number of III be I the structural unit number 1～80%, the structural unit number of IV be I the structural unit number 1～15%, the structural unit number of [I+IV]: structural unit number=1 of [II+III], the segment of each structural unit or its formation is to be connected combination by carboxyl arbitrarily with hydroxy functional group, and the intrinsic viscosity of this flame-proof copolyester [η] is 0.40～0.99dL/g, fusing point is 100-220 ℃, and oxygen index is 28～48%, vertical combustion grade V-0.
2, low-melting point phosphor-containing flame-retardant copolyester according to claim 1, in this flame-proof copolyester the structural unit number of III be I the structural unit number 2～75%, the structural unit number of IV be I the structural unit number 1～10%, the structural unit number of [I+IV]: structural unit number=1 of [II+III].
3, a kind of method for preparing each described low-melting point phosphor-containing flame-retardant copolyester in the claim 1～2, this method is with terephthalic acid or its carboxylate and ethylene glycol, catalyzer proportioning routinely, after adopting direct esterification method or ester-interchange method to carry out esterification, be prepared from through polycondensation, it is characterized in that before esterification or the esterification aftercondensated before, add in reaction system by the molecular fraction of diprotic acid or its carboxylate and count 1～80% the 3rd monomer and 1～15% the 4th monomer, wherein the 3rd monomeric general structure is as follows:
HO-R
2·OH
In the formula, R
2Be C
3～C
8Straight or branched alkyl, the 4th monomer are response type phosphor-containing flame-proof monomer.
4, the preparation method of low-melting point phosphor-containing flame-retardant copolyester according to claim 3, it is characterized in that this method before esterification or before the esterification aftercondensated, in reaction system, add by the molecular fraction of diprotic acid or its carboxylate and count 2～75% the 3rd monomer and 1～10% response type phosphor-containing flame-proof monomer.
5,, it is characterized in that the used response type phosphor-containing flame-proof monomer of this method is the compound with following general structure according to the preparation method of claim 3 or 4 described low-melting point phosphor-containing flame-retardant copolyesters:
In the formula, R
3Be C
1～C
12Straight or branched alkyl, aryl or benzyl, R
4Be C
1～C
8Straight or branched alkylidene group, aryl or fatty aryl radical, X represents O or S atom,
Perhaps for having 9 of following general structure, the 10-dihydro-9-oxy is mixed-the assorted luxuriant and rich with fragrance compounds of 10-phosphono:
In the formula, Y represents O or S atom, Z
1, Z
2Be hydroxy-acid group or ester group group, Z
1, Z
2Identical or inequality.
6, the preparation method of low-melting point phosphor-containing flame-retardant copolyester according to claim 5, it is characterized in that the response type phosphor-containing flame-proof monomer 9 that this method is used, the 10-dihydro-9-oxy is assorted-the assorted luxuriant and rich with fragrance compounds of 10-phosphono in the ester group group be the methyl esters group after the monohydroxy-alcohol esterification or be the glycol ester group behind the dibasic alcohol ester.
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