CN101186688A - Fire resistant polyester with excellent hydrolytic resistance capability and preparation method thereof - Google Patents
Fire resistant polyester with excellent hydrolytic resistance capability and preparation method thereof Download PDFInfo
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- CN101186688A CN101186688A CNA2006100976387A CN200610097638A CN101186688A CN 101186688 A CN101186688 A CN 101186688A CN A2006100976387 A CNA2006100976387 A CN A2006100976387A CN 200610097638 A CN200610097638 A CN 200610097638A CN 101186688 A CN101186688 A CN 101186688A
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- naphthalene
- polyester
- hydrolytic resistance
- organophosphorus
- flame retardant
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Abstract
The invention discloses flame-retarded polyester with excellent hydrolytic resistance, which is copolyester of polyterephthalic acid gylcol ester containing naphthalene unit and organophosphorus, wherein the copolyester is copolymerized by naphthalene monomer and terephthalic acid or dimethyl terephthalates, ethylene glycol and organophosphorus. The obtained polyester of the invention has excellent hydrolytic resistance and fire-retardancy, which solves the problem of poor hydrolytic resistance due to phosphorus-containing copolymerized flame retardant resin.
Description
Technical field:
The present invention relates to a kind of polyester and production method, is a kind of hydrolysis flame retardant polyester and production method.
Background technology:
Polyester product particularly polyethylene terephthalate has become the product of chemical fibre industry output maximum in the world owing to the field that its excellent performance is widely used in making fiber and goods thereof.Along with the mankind to the raising of the requirement of quality of life with to the enhancing of autoprotection consciousness; requirement to polyester product is also more and more higher; the particularly requirement of safety in utilization aspect; as require polyester product to have good flame retardancy; so that under the situation of catching fire; can not bring bigger disaster, so the polyester that the numerous and confused exploitation of each company has flame retardant properties to the mankind.
The flame-retarded technology of each company's use mainly contains post-treatment technology, copolymerization, blending technology etc. at present.The post-treatment technology is mainly carried out coating processing etc. to trevira or polyester textile, but has a unabiding shortcoming of flame retardant effect, and aspects such as the dyeing of product, feel are produced a lot of influences.
Chinese patent 02817032.6 adopts the method for blend to obtain fire-retardant PET, is to use brominated based flame retardant, though reached flame retardant properties, brominated flame-retardant can produce toxic smog in combustion processes, banned use of by many countries gradually.Other companies also adopt non-halogen fire retardant to be used for blend, but blending technology is that the polyester of producing is carried out secondary processing, need extra production to product to increase cost.
Each company also develops the copolymerization flame-retarded technology, gives polyester good combustion-supporting performance from essential structure.It is that comonomer adds the pet reaction system in polycondensation phase that Chinese patent 00804393.0, Chinese patent 02109909.X are to use organophosphorus, thereby obtain the copoly type flame retardant polyester, but this type polyester is total to fire retardant at the fire retardant that uses as phosphoric acid ester, the existence owing to phosphoric acid ester of synthetic back polyester, make the polyester can not hydrolysis, making the processing of fiber post-treatment for polyester, particularly high temperature dyeing has brought very big difficulty.
Summary of the invention:
The object of the present invention is to provide that a kind of flame retardant properties is good, excellent hydrolysis resistance have fire-retardant polyester of excellent hydrolytic resistance capability and preparation method thereof.
Technical solution of the present invention is:
A kind of flame retardant polyester with excellent hydrolytic resistance capability, it is characterized in that: be the copolyesters that contains unitary polyethylene terephthalate of naphthalene and organophosphorus, obtain through polymerization by naphthalene monomer and terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, organophosphorus.
The naphthalene monomer is naphthalene diacid or its ester derivative, and the unitary content of naphthalene is 2%～50% of naphthalene unit and terephthalic acid sum by molar weight in the copolyesters.
In polyester, add and have the naphthalene unit that the excellent in resistance hydrolysis contains big aromatic group, thereby make whole polyester with the phosphoric acid ester copolymerization after, good characteristic with hydrolysis, the polyester that the present invention selects for use is a polyethylene terephthalate, the naphthalene monomer can be selected from 2,6--naphthalene diacid and ester derivative thereof, 1,4-naphthalene diacid and ester derivative thereof, 1,5-naphthalene diacid and ester derivative thereof.Preferred 2,6-naphthalene diacid and ester derivative thereof, as 2,6-naphthalene diacid, 2,6-naphthalene two dimethyl phthalates.
The organophosphorus monomer is the compound with following structural formula:
The organophosphorus multipolymer that contains the 2-20 weight part in the copolyesters of per 100 weight parts.
A kind of preparation method with flame retardant polyester of excellent hydrolytic resistance capability comprises the synthetic of polyester, it is characterized in that: esterification or the adding of transesterify stage at synthesizing polyester contain the naphthalene monomer, add the organophosphorus monomer in esterification or polycondensation phase.
The organophosphorus monomer is at first made the ethylene glycol solution that concentration is the organo phosphorous compounds of 40-70% with glycol reaction, adds the pet reaction system in Esterification Stage or polycondensation phase then.
Synthetic method for copolyesters specifically can adopt following synthetic method: at first adding conventional catalysts such as raw material terephthalic acid, ethylene glycol, naphthalene diacid carry out esterification or transesterification reaction, the back is being warming up to 270～300 ℃, add the conventional polycondensation catalyst of antimony or titanium class and under high vacuum condition, carry out polycondensation, after arriving the molecular weight that needs, obtain the multipolymer that needs.Wherein polymerization process can be successive polymerization, also can be non-successive polymerization.Reaction conditions wherein is synthetic identical with normal polyester.
It is preferred 5%～50% to contain the monomeric addition of naphthalene, and the rigidity that addition is crossed copolyesters at most is too strong, influences processing, the application performance of the finished product fiber; Addition is crossed the low fine hydrolysis effect that then can not obtain.
For selection of fire retardant, the present invention selects the DDP of phosphoric on side chain as comonomer, and the phosphoric acid ester bond has just been stayed on the side chain of PET like this, the strong not situation of hydrolysis of the fire-retardant polyester that causes owing to phosphoric acid ester bond facile hydrolysis of having avoided.Use the ethylene glycol solution that makes DDP second diester prior to glycol reaction for DDP the present invention, the concentration of solution is 40%～70%, preferred 50%～65%.
The addition of DDP is 2%～20% in final copolymer, and addition is crossed and do not reached flame retardant properties at least, and addition is greater than 20%, and then the fusing point of copolyesters descends too much, influences the processing characteristics of product.
Fire-retardant monomeric interpolation can be to add in esterification (transesterification reaction) stage at copolyesters also can add at polymerization stage, preferably after the esterification (transesterification reaction) of copolyesters finishes, adds reaction system before the polycondensation.
Not influencing under the fire-retardant prerequisite with resistance to hydrolysis of the present invention, in polyester of the present invention, can also add conventional antioxidant, anti ultraviolet agent, white dyes, heat-resistant agent, toning agent etc.
The invention will be further described below in conjunction with embodiment:
Embodiment 1:
The oxalic acid solution of DDP (by this grease production of bamboo);
Modulation ethylene glycol and terephthalic acid and 2, the raw slurry of 6-naphthalene diacid, acid is 1: 1.15 with the mol ratio of alcohol, wherein the mol ratio of naphthalene diacid in diacid is 25%.In having the esterifier of agitator, under 250 ℃, go out dereaction and remove the water that reaction produces, when the esterification rate reaches 90% or surpass 90% back end esterification.Add in the reaction soln containing the ethylene glycol solution that is equivalent to final polyester 8% weight DDP, add trimethyl phosphate then as stablizer, ANTIMONY TRIOXIDE SB 203 99.8 PCT is as polycondensation catalyst, Cobaltous diacetate is a toning agent, be warmed up to 290 ℃, and the vacuum that reduces pressure in 100 minutes is to carry out polycondensation below the 200Pa, wait reach target molecular weight after, obtain having the flame retardant polyester of excellent hydrolytic resistance capability.
Embodiment 2:
Modulation ethylene glycol and dimethyl terephthalate (DMT) and 2, the raw slurry of 6-naphthalene two dimethyl phthalates, two kinds of dimethyl esters and pure mol ratio are 1: 1.9, wherein the mol ratio of naphthalene two dimethyl phthalates in dimethyl ester is 30%.In having the esterifier of agitator, under 250 ℃, go out dereaction and remove the methyl alcohol that reaction produces, when the transesterification reaction rate reaches 90% or surpass 90% back end esterification.The ethylene glycol solution that is equivalent to the DDP of final polyester 11% weight ratio is added in the reaction soln, add trimethyl phosphate then as stablizer, ANTIMONY TRIOXIDE SB 203 99.8 PCT is as polycondensation catalyst, Cobaltous diacetate is a toning agent, be warmed up to 290 ℃, and the vacuum that reduces pressure in 100 minutes is to carry out polycondensation below the 200Pa, wait reach target molecular weight after, obtain having the flame retardant polyester of excellent hydrolytic resistance capability.
Embodiment 3:
The mol ratio of the amount of naphthalene diacid in diacid is 15%, and the DDP add-on is to be equivalent to 10% of final weight polyester.All the other are with embodiment 1.
Embodiment 4:
The mol ratio of the amount of naphthalene diacid in diacid is 10%, and the DDP add-on is to be equivalent to 5% of final weight polyester.All the other are with embodiment 1.
Embodiment 5:
A kind of preparation method with flame retardant polyester of excellent hydrolytic resistance capability comprises the synthetic of polyester, adds in the esterification of synthesizing polyester or transesterify stage and contains the naphthalene monomer, adds the organophosphorus monomer in esterification or polycondensation phase.The organophosphorus monomer is at first made the ethylene glycol solution that concentration is the organo phosphorous compounds of 40-70% (example 40%, 55%, 70%) with glycol reaction, adds the pet reaction system in Esterification Stage or polycondensation phase then.
Naphthalene monomer 2,6--naphthalene diacid or its ester derivative (or 1,4-naphthalene diacid or its ester derivative or 1,5-naphthalene diacid or ester derivative, preferred 2,6-naphthalene diacid, 2,6-naphthalene two dimethyl phthalates).
The unitary content of naphthalene is 2%～50% (example 2%, 30%, 50%) of naphthalene unit and terephthalic acid sum by molar weight in the copolyesters.
The organophosphorus monomer is the compound with following structural formula:
(DDP); Wherein R, R ' group are hydrogen atom (or methyl or ethyl or hydroxyethyl or hydroxyl normal-butyl or hydroxypropyls).The organophosphorus multipolymer that contains 2-20 weight part (example 2 weight parts, 12 weight parts, 20 weight parts) in the copolyesters of per 100 weight parts.
Comparative example 1:
Experimental installation and method still do not have naphthalene diacid interpolymer with embodiment 1, and DDP is 7% in the amount of final polyester.
Comparative example 2:
Experimental installation and method are with embodiment 2, and the amount of naphthalene diacid is 30%, but DDP is 0 in the amount of final polyester.
Evaluation result:
| The naphthalene quantity of units | The amount of DDP | Limiting viscosity | The LOI value | ％BB | |
| Embodiment 1 | 25％ | 8％ | 0.66 | 30 | 0.20 |
| Embodiment 2 | 30％ | 8％ | 0.65 | 30 | 0.15 |
| Embodiment 3 | 15％ | 10％ | 0.64 | 31 | 0.25 |
| Embodiment 4 | 10％ | 5％ | 0.64 | 29 | 0.28 |
| Comparative example 1 | 0 | 7％ | 0.66 | 29 | 0.45 |
| Comparative example 2 | 30％ | 0％ | 0.65 | 23 | 0.13 |
Evaluation method:
Limiting viscosity:
It is in phenol/sym.-tetrachloroethane mixed solvent of 3: 2, to test at Ubbelohde viscometer under 30 ℃ of conditions that polyester is dissolved in weight ratio.
％BB：
Polyester is soaked in the enclosed system of 130 degree water after 6 hours, the ratio of ester linkage breaking, its numerical value can calculate by following formula: %B B=0.244 * { [η
a]
-1.471-[η
b]
-1.471; [η
a] for soaking limiting viscosity afterwards, [η
b] for soaking limiting viscosity before.
The LOI value:
Measure with oxygen index (LOI) determinator.
Claims (6)
1. flame retardant polyester with excellent hydrolytic resistance capability, it is characterized in that: be the copolyesters that contains unitary polyethylene terephthalate of naphthalene and organophosphorus, obtain through polymerization by naphthalene monomer and terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, organophosphorus.
2. the flame retardant polyester with excellent hydrolytic resistance capability according to claim 1 is characterized in that: the naphthalene monomer is naphthalene diacid or its ester derivative, and the unitary content of naphthalene is 2%～50% of naphthalene unit and terephthalic acid sum by molar weight in the copolyesters.
3. the flame retardant polyester with excellent hydrolytic resistance capability according to claim 1 is characterized in that: the organophosphorus monomer is the compound with following structural formula:
4. the flame retardant polyester with excellent hydrolytic resistance capability according to claim 3 is characterized in that: the organophosphorus multipolymer that contains the 2-20 weight part in the copolyesters of per 100 weight parts.
5. the preparation method with flame retardant polyester of excellent hydrolytic resistance capability comprises the synthetic of polyester, it is characterized in that: esterification or the adding of transesterify stage at synthesizing polyester contain the naphthalene monomer, add the organophosphorus monomer in esterification or polycondensation phase.
6. the preparation method with flame retardant polyester of excellent hydrolytic resistance capability according to claim 5, it is characterized in that: the organophosphorus monomer is at first made the ethylene glycol solution that concentration is the organo phosphorous compounds of 40-70% with glycol reaction, adds the pet reaction system in Esterification Stage or polycondensation phase then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100976387A CN101186688A (en) | 2006-11-15 | 2006-11-15 | Fire resistant polyester with excellent hydrolytic resistance capability and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100976387A CN101186688A (en) | 2006-11-15 | 2006-11-15 | Fire resistant polyester with excellent hydrolytic resistance capability and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101186688A true CN101186688A (en) | 2008-05-28 |
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|---|---|---|---|
| CNA2006100976387A Pending CN101186688A (en) | 2006-11-15 | 2006-11-15 | Fire resistant polyester with excellent hydrolytic resistance capability and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264795B (en) * | 2008-12-31 | 2014-03-12 | Sk化学株式会社 | Method for preparing polyester resin |
| WO2014089806A1 (en) * | 2012-12-13 | 2014-06-19 | Sabic Innovative Plastics Ip B.V. | Flame retardant polyester composition |
| CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
-
2006
- 2006-11-15 CN CNA2006100976387A patent/CN101186688A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264795B (en) * | 2008-12-31 | 2014-03-12 | Sk化学株式会社 | Method for preparing polyester resin |
| WO2014089806A1 (en) * | 2012-12-13 | 2014-06-19 | Sabic Innovative Plastics Ip B.V. | Flame retardant polyester composition |
| US9428643B2 (en) | 2012-12-13 | 2016-08-30 | Sabic Global Technologies B.V. | Flame retardant polyester composition |
| CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
| CN114634688B (en) * | 2022-04-26 | 2023-09-01 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
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Open date: 20080528 |