CN102532498B - Thioether-containing self-flame-retardant polyester and preparation method thereof - Google Patents
Thioether-containing self-flame-retardant polyester and preparation method thereof Download PDFInfo
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- CN102532498B CN102532498B CN 201210029882 CN201210029882A CN102532498B CN 102532498 B CN102532498 B CN 102532498B CN 201210029882 CN201210029882 CN 201210029882 CN 201210029882 A CN201210029882 A CN 201210029882A CN 102532498 B CN102532498 B CN 102532498B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 37
- 229920000728 polyester Polymers 0.000 title claims abstract description 36
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 dimethyl chloride Chemical compound 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 229920001225 polyester resin Polymers 0.000 claims abstract description 4
- 239000004645 polyester resin Substances 0.000 claims abstract description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 16
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 11
- IUCFPVGNXLLCNG-UHFFFAOYSA-N OC1=CC=C(C=C1)C(C)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound OC1=CC=C(C=C1)C(C)P(C1=CC=CC=C1)C1=CC=CC=C1 IUCFPVGNXLLCNG-UHFFFAOYSA-N 0.000 description 7
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Abstract
The invention discloses thioether-containing self-flame-retardant polyester and a preparation method thereof. The preparation method is characterized by comprising the following steps: successively adding 28.4-29 parts of diphenol monomer, 0.1-10 parts of catalyst and 8-20 parts of alkali into a three-necked flask filled with 30-200 parts of water, and stirring and dissolving at room temperature; dissolving 20-40 parts of 4,4'-diphenyl thioether dimethyl chloride into a beaker filled with 50-300 parts of organic solvent, and dropwise adding the mixture into the three-necked flask, and stirring and reacting for 3-10 hours at the temperature of 5-35 DEG C so as to obtain high-molecular-weight thioether-containing polyester resin; and washing the polymer with water and ethanol, drying for 2-8 hours at the temperature of 50-200 DEG C, smashing, extracting and purifying with deionized water and acetone respectively, drying for 1-20 hours at the temperature of 80-200 DEG C so as to obtain the pure thioether-containing self-flame-retardant polyester resin.
Description
Technical field
The present invention relates to a kind of thioether-containing self-flame-retardant polyester and preparation method thereof, belong to the Polymer Synthesizing field.
Background technology
aromatic polyester has excellent thermal characteristics (high glass transition temperature and fusing point), mechanical strength etc., but it is often because the high rigidity of molecular chain is difficult to by traditional processing mode forming process (Bhowmik, P.K., Han, H.Macromolecules, 1993, 26, 5287.), and polyphenylene sulfide has good processibility and corrosion resistance nature etc., (Yang Jie edits but its second-order transition temperature is on the low side (85 ℃), polyphenylene sulfide and application thereof, Chemical Industry Press, 2006), advantage for comprehensive polyphenylene sulfide and two kinds of polymkeric substance of aromatic polyester, improve the second-order transition temperature of poly arylidene thio-ester, improve the aromatic polyester workability poor, inflammable shortcoming, keep simultaneously its excellent thermal characteristics, we are incorporated into the soft segment thioether bond in the aromatic polyester molecular backbone chain, design has prepared this base polymer of thioether-containing self-flame-retardant polyester.
Summary of the invention
The objective of the invention is provides a kind of thioether-containing self-flame-retardant polyester polymkeric substance and preparation method thereof for the deficiencies in the prior art, be characterized in diphenol monomer and Sulfide-containing Hindered dimethyl chloride monomer are carried out polycondensation, overcome the low aromatic polyester that reaches of polyphenylene sulfide glass temperature and be difficult to forming process and inflammable defective, the method has advantages of that yield is high, molecular weight is higher, easy processing, high temperature resistant, corrosion-resistant, fire-retardant.
Purpose of the present invention realizes by following technical measures, and wherein said raw material umber is parts by weight except specified otherwise.
The starting raw material of thioether-containing self-flame-retardant polyester is composed of the following components:
Wherein, the diphenol monomer is two (4-the hydroxyphenyl)-1-diphenylphosphino ethanes of 1,1-or two (3, the 5-dimethyl-4-hydroxyphenyl) propane of 2,2-.
Catalyzer is any in Tetrabutyl amonium bromide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Sodium dodecylbenzene sulfonate, benzene sulfonic acid sodium salt, sodium alginate or sodium laurylsulfonate.
Alkali is any in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus.
Organic solvent is any in 1,2-ethylene dichloride, methylene dichloride, chloroform, hexanaphthene, pimelinketone, chlorobenzene or Meta Dichlorobenzene.
The preparation method of thioether-containing self-flame-retardant polyester comprises the following steps:
(1). the preparation of thioether-containing self-flame-retardant polyester
With 28.4～29 parts of diphenol monomers, 0.1～10 part of catalyzer, 8～20 parts, alkali joins in the three-necked flask that 30～200 parts of water are housed stirring and dissolving under room temperature successively; Again with 4,4 '-diphenylsulfide dimethyl chloride 20-40 part is dissolved in the beaker that 50～300 parts of organic solvents are housed, and drops in above-mentioned three-necked flask, in 5～35 ℃ of stirring reaction 3～10h, obtain the thioether-containing self-flame-retardant polyester resin of high molecular, its structural formula is:
Wherein, n=10-300
(2). the purifying of thioether-containing self-flame-retardant polyester
Above-mentioned polymkeric substance through water, washing with alcohol, in 50～200 ℃ of drying 2～8h of temperature, is pulverized, then purified with deionized water, acetone extract respectively, in 80～200 ℃ of drying 1～20h of temperature, obtain the thioether-containing self-flame-retardant polyester virgin resin.
Performance test
1, the structure of the thioether-containing self-flame-retardant polyester of the present invention preparation through examination of infrared spectrum and
1H-NMR has obtained confirmation, as Fig. 1～shown in Figure 3.
2, by regulation and control reactant concn, material proportion and temperature of reaction, the thioether-containing self-flame-retardant polyester of preparation different viscosity; And take NMP as solvent, the sample liquid of preparation 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature with the intrinsic viscosity of determination of ubbelohde viscometer polymkeric substance=0.70～1.3dl/g.
3, polymkeric substance has been carried out respectively the test of solubility experiment and flame retardant properties, the results detailed in Table 1, shown in table 2.
4, adopt the thermostability of thermogravimetic analysis (TGA) method (TGA) test thioether-containing self-flame-retardant polyester, the results detailed in shown in Figure 4.
5, adopt the second-order transition temperature of differential scanning calorimetric analysis method (DSC) test thioether-containing self-flame-retardant polyester, the results detailed in shown in Figure 5.
The present invention has following advantage:
1. adopt the dimethyl chloride that contains sulfide based structural as reaction monomers, due to the introducing of soft segment thioether bond, effectively improve the solvability of polymkeric substance in solvent, thereby obtain the more resin of high molecular; The introducing of thioether bond simultaneously can improve the hot workability of resin, greatly improves the flame retardant properties of polymkeric substance.
2. what adopt in polymerization process is the room temperature interfacial polymerization, avoided the waste of high temperature polymerization to the energy, it is simple that it has technique, and security is good, repeatability is strong, good stability, molecular weight product is high, yield is high, purity is high, pollutes little and the easy advantage such as recovery of solvent.
3. this base polymer is used for special engineering plastics and high performance polymer matrix material and prepares heat-resisting, rub resistance, fire-retardant parts and goods; Due to its excellent fluidity of molten also for the preparation of the structural part of configuration complexity.
Description of drawings:
Fig. 1 is poly-4,4 '-diphenylsulfide dioctyl phthalate 2, two (3,5-dimethyl-4-hydroxyphenyl) the propane esters of 2----TDC-TMBPA and poly-4,4 '-diphenylsulfide dioctyl phthalate 1, two (4-hydroxyphenyl)-1-diphenylphosphino ethane ester---the infrared spectrums of TDC-PhBPA of 1-:
3060cm wherein
-1Neighbouring is the vibration absorption peak of phenyl ring C-H, 2960cm
-1, 2860cm
-1Near be-CH
3Stretching vibration absorb, 1735cm
-1Near be-absorption peak of COO-, 1590cm
-1, 1540cm
-1, 1500cm
-1Neighbouring is the skeleton absorption peak of phenyl ring, 1080cm
-1Near be-absorption peak of S-.
Fig. 2 is poly-4,4 '-diphenylsulfide dioctyl phthalate 2, two (3,5-dimethyl-4-hydroxyphenyl) propane ester---the nuclear magnetic spectrograms of TDC-TMBPA of 2-:
Gather 4,4 '-diphenylsulfide dioctyl phthalate 2, two (3,5-dimethyl-4-hydroxyphenyl) the propane esters of 2----TDC-TMBPA's
1H-NMR, take deuterated dimethyl sulfoxide (DMSO) as solvent, wherein the ownership at each peak is indicated respectively in the drawings.
Fig. 3 is poly-4,4 '-diphenylsulfide dioctyl phthalate 1, two (4-hydroxyphenyl)-1-diphenylphosphino ethane ester---the nuclear magnetic spectrograms of TDC-PhBPA of 1-:
Gather 4,4 '-diphenylsulfide dioctyl phthalate 1, two (4-the hydroxyphenyl)-1-diphenylphosphino ethane esters of 1----TDC-PhBPA's
1H-NMR, take deuterated dimethyl sulfoxide (DMSO) as solvent, wherein the ownership at each peak is indicated respectively in the drawings.
Fig. 4 is the thermogravimetric curve of thioether-containing self-flame-retardant polyester in nitrogen atmosphere.
Fig. 5 is differential scanning calorimetric analysis (DSC) curve of thioether-containing self-flame-retardant polyester in nitrogen atmosphere.
Embodiment
Below by embodiment, the present invention is carried out concrete description, be necessary to be pointed out that at this present embodiment only is used for the present invention is further illustrated, can not be interpreted as that the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above to the present invention includes the restriction of scope.
With two (3,5-dimethyl-4-hydroxyphenyl) the propane 28.4g of 2,2-, palmityl trimethyl ammonium chloride 10g, salt of wormwood 13.8g joins in the three-necked flask that 200g water is housed stirring and dissolving under room temperature successively; Again with 4,4 '-diphenylsulfide dimethyl chloride 20g is dissolved in the beaker that 300 parts of methylene dichloride are housed, and drop in above-mentioned three-necked flask, in 35 ℃ of stirring reaction 10h, obtain the Sulfide-containing Hindered polyester poly-4 of high molecular, 4 '-diphenylsulfide dioctyl phthalate 2,2-two (3,5-dimethyl-4-hydroxyphenyl) propane ester---TDC-TMBPA is through water, washing with alcohol, in 50 ℃ of dry 8h, pulverize, purify with deionized water, acetone extract respectively, obtain virgin resin 47.4g in 100 ℃ of dry 5h, productive rate is about 92%; Be that the solvent configuration concentration is the solution of 0.5g/dl with chloroform, use Ubbelohde viscometer at 30.0 ± 0.1 ℃ of temperature, measure intrinsic viscosity=0.7dl/g, infrared and nuclear-magnetism characterizes and sees respectively Fig. 1, shown in Figure 2 for details, thermogravimetic analysis (TGA) is as shown in Figure 4: its hot temperature of initial decomposition is 402.3 ℃, the carbon residue amount of 800 ℃ is 35.0%, dsc analysis as shown in Figure 5: its second-order transition temperature is 216.9 ℃, has thermal characteristics preferably; Solvent resistance is as shown in Table 1 below, and flame retardant properties is as shown in Table 2 below.
With two (4-the hydroxyphenyl)-1-diphenylphosphino ethane 29g of 1,1-, sodium laurylsulfonate 5g, saleratus 20g joins in the three-necked flask that 100g water is housed stirring and dissolving under room temperature successively; With 4,4 '-diphenylsulfide dimethyl chloride 40g is dissolved in the beaker that 150 parts of chloroforms are housed, and drops in three-necked flask again, in 25 ℃ of stirring reaction 5h, the Sulfide-containing Hindered polyester that obtains high molecular gathers 4,4 '-diphenylsulfide dioctyl phthalate 1, two (4-hydroxyphenyl)-1-diphenylphosphino ethane ester---the TDC-PhBPA of 1-, through water, washing with alcohol, in 100 ℃ of dry 5h, pulverize, then purify with deionized water, acetone extract respectively, obtain virgin resin 50.6g in 200 ℃ of dry 1h, productive rate is about 96%; Be that the solvent configuration concentration is the solution of 0.5g/dl with the vitriol oil, use Ubbelohde viscometer at 30.0 ± 0.1 ℃ of temperature, measure intrinsic viscosity=1.3dl/g, infrared and nuclear-magnetism characterizes and sees respectively Fig. 1, shown in Figure 3 for details, thermogravimetic analysis (TGA) is as shown in Figure 4: its hot temperature of initial decomposition is 447.9 ℃, the carbon residue amount of 800 ℃ is 39.8%, dsc analysis as shown in Figure 5: its second-order transition temperature is 235.6 ℃, has thermal characteristics preferably; Solvent resistance is as shown in Table 1 below, and flame retardant properties is as shown in Table 2 below.
With two (3,5-dimethyl-4-hydroxyphenyl) the propane 28.5g of 2,2-, cetyl trimethylammonium bromide 0.1g, sodium hydroxide 8g joins in the three-necked flask that 30g water is housed stirring and dissolving under room temperature successively; Again with 4,4 '-diphenylsulfide dimethyl chloride 30g is dissolved in the beaker that 50 parts of chlorobenzenes are housed, and drop in above-mentioned three-necked flask, in 5 ℃ of stirring reaction 3h, obtain the Sulfide-containing Hindered polyester poly-4 of high molecular, 4 '-diphenylsulfide dioctyl phthalate 2,2-two (3,5-dimethyl-4-hydroxyphenyl) propane ester---TDC-TMBPA is through water, washing with alcohol, in 200 ℃ of dry 2h, pulverize, purify with deionized water, acetone extract respectively, obtain virgin resin 46.3g in 80 ℃ of dry 20h, productive rate is about 93%; Be that the solvent configuration concentration is the solution of 0.5g/dl with chloroform, use Ubbelohde viscometer at 30.0 ± 0.1 ℃ of temperature, measure intrinsic viscosity=0.9dl/g.
With two (4-the hydroxyphenyl)-1-diphenylphosphino ethane 28.8g of 1,1-, sodium alginate 3g, potassium hydroxide 10g joins in the three-necked flask that 80g water is housed stirring and dissolving under room temperature successively; Again with 4,4 '-diphenylsulfide dimethyl chloride 36g is dissolved in the beaker that 100 parts of hexanaphthenes are housed, and drop in three-necked flask, in 30 ℃ of stirring reaction 6h, obtain the Sulfide-containing Hindered polyester poly-4 of high molecular, 4 '-diphenylsulfide dioctyl phthalate 1, two (4-hydroxyphenyl)-1-diphenylphosphino ethane ester---the TDC-PhBPA of 1-, through water, washing with alcohol, in 120 ℃ of dry 3h, pulverize, then purify with deionized water, acetone extract respectively, obtain virgin resin 49.7g in 100 ℃ of dry 10h, productive rate is about 95%; Be that the solvent configuration concentration is the solution of 0.5g/dl with the vitriol oil, use Ubbelohde viscometer at 30.0 ± 0.1 ℃ of temperature, measure intrinsic viscosity=1.2dl/g.
Table 1 is the solubility experiment form of thioether-containing self-flame-retardant polyester
*
*In table 1+be that room temperature is solvable; +-be room temperature slightly soluble;-be that room temperature is insoluble;
Table 2 is the flame retardant properties experiment form of thioether-containing self-flame-retardant polyester
*
*In table 21, poly-4,4 '-diphenylsulfide dioctyl phthalate 2, two (3,5-dimethyl-4-hydroxyphenyl) propane ester---the TDC-TMBPA of 2-; 2, gather 4,4 '-diphenylsulfide dioctyl phthalate 1, two (4-hydroxyphenyl)-1-diphenylphosphino ethane ester---the TDC-PhBPA of 1-.
Claims (4)
1. a thioether-containing self-flame-retardant polyester, is characterized in that the starting raw material of this thioether-containing self-flame-retardant polyester is composed of the following components, is by weight:
28.4～29 parts of diphenol monomers
0.1～10 part of catalyzer
8～20 parts, alkali
30～200 parts, water
4,4 '-diphenylsulfide dimethyl chloride 20-40 part
50～300 parts of organic solvents
Wherein, the diphenol monomer is two (4-the hydroxyphenyl)-1-diphenylphosphino ethanes of 1,1-or two (3, the 5-dimethyl-4-hydroxyphenyl) propane of 2,2-;
And by following processing step and parameter preparation
(1). the preparation of thioether-containing self-flame-retardant polyester
With 28.4～29 parts of diphenol monomers, 0.1～10 part of catalyzer, 8～20 parts, alkali adds in the three-necked flask that 30～200 parts of water are housed stirring and dissolving under room temperature successively; Again with 4,4 '-diphenylsulfide dimethyl chloride 20-40 part is dissolved in the beaker that 50～300 parts of organic solvents are housed, and drops in above-mentioned three-necked flask, in 5～35 ℃ of stirring reaction 3～10h of temperature, obtain the thioether-containing self-flame-retardant polyester resin of high molecular, its structural formula is:
Wherein, n=10-300
(2). the purifying of thioether-containing self-flame-retardant polyester
Above-mentioned polymkeric substance through water, washing with alcohol, in 50～200 ℃ of drying 2～8h of temperature, is pulverized, then purified with deionized water, acetone extract respectively, in 80～200 ℃ of drying 1～20h of temperature, obtain the thioether-containing self-flame-retardant polyester virgin resin.
2. thioether-containing self-flame-retardant polyester as claimed in claim 1, is characterized in that catalyzer is any in Tetrabutyl amonium bromide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Sodium dodecylbenzene sulfonate, benzene sulfonic acid sodium salt, sodium alginate or sodium laurylsulfonate.
3. thioether-containing self-flame-retardant polyester as claimed in claim 1, is characterized in that alkali is any in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus.
4. thioether-containing self-flame-retardant polyester as claimed in claim 1, is characterized in that organic solvent is any in 1,2-ethylene dichloride, methylene dichloride, chloroform, hexanaphthene, pimelinketone, chlorobenzene or Meta Dichlorobenzene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665137A (en) * | 1984-03-06 | 1987-05-12 | The B. F. Goodrich Company | Crosslinkable difunctionalized poly(phenylene oxide) and process for preparation thereof |
| CN1660776A (en) * | 2004-12-16 | 2005-08-31 | 上海交通大学 | Compound of aroma dihydroxy diamines and preparation method |
| CN101367937A (en) * | 2008-10-15 | 2009-02-18 | 东华大学 | Preparation method for synthesizing soluble polyimide in polyphosphoric acids |
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| JP4788896B2 (en) * | 2006-02-22 | 2011-10-05 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665137A (en) * | 1984-03-06 | 1987-05-12 | The B. F. Goodrich Company | Crosslinkable difunctionalized poly(phenylene oxide) and process for preparation thereof |
| CN1660776A (en) * | 2004-12-16 | 2005-08-31 | 上海交通大学 | Compound of aroma dihydroxy diamines and preparation method |
| CN101367937A (en) * | 2008-10-15 | 2009-02-18 | 东华大学 | Preparation method for synthesizing soluble polyimide in polyphosphoric acids |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2007-225791A 2007.09.06 |
| 聚芳硫醚酮酰胺树脂的合成与表征;黄光顺等;《功能材料》;20111231;第42卷(第6期);1041-1044 * |
| 黄光顺等.聚芳硫醚酮酰胺树脂的合成与表征.《功能材料》.2011,第42卷(第6期),1041-1044. |
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