TWI408144B - Flame retardant polyester copolymer - Google Patents
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- TWI408144B TWI408144B TW99146962A TW99146962A TWI408144B TW I408144 B TWI408144 B TW I408144B TW 99146962 A TW99146962 A TW 99146962A TW 99146962 A TW99146962 A TW 99146962A TW I408144 B TWI408144 B TW I408144B
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- 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 title claims abstract description 51
- 239000003063 flame retardant Substances 0.000 title claims abstract description 51
- 229920000728 polyester Polymers 0.000 title claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 67
- 239000011574 phosphorus Substances 0.000 claims abstract description 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229920001577 copolymer Polymers 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- 239000000178 monomer Substances 0.000 abstract description 19
- 150000002009 diols Chemical class 0.000 abstract description 11
- 150000002148 esters Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- -1 phosphorus compound Chemical class 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229940011182 cobalt acetate Drugs 0.000 description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 3
- VOFOZYPOSUYPPG-UHFFFAOYSA-N 2,3-bis(2-hydroxyethyl)naphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(CCO)C(CCO)=CC2=C1 VOFOZYPOSUYPPG-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 210000003739 neck Anatomy 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N benzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- FUZUFZCLXLEROD-UHFFFAOYSA-N bis(4-hydroxybutyl) benzene-1,2-dicarboxylate Chemical compound OCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCO FUZUFZCLXLEROD-UHFFFAOYSA-N 0.000 description 1
- 229940067596 butylparaben Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本發明是有關於一種磷系二醇單體及其難燃聚酯共聚物，且特別是有關於一種以磷系二醇為組成單體之難燃磷系聚酯共聚物。The present invention relates to a phosphorus-based diol monomer and a flame-retardant polyester copolymer thereof, and more particularly to a flame-retardant phosphorus-based polyester copolymer comprising a phosphorus-based diol as a constituent monomer.
聚酯(polyester)為重要的塑膠材料，其具有良好的機械及化學特性，被廣泛地應用於合成纖維、織物、薄膜等相關產業。由於聚酯高分子大量應用於民生相關產業，因此合成纖維的耐燃特性逐漸受到重視。Polyester is an important plastic material with good mechanical and chemical properties and is widely used in synthetic fibers, fabrics, films and other related industries. Since polyester polymers are widely used in people's livelihood-related industries, the flame resistance characteristics of synthetic fibers are gradually receiving attention.
為使聚酯高分子達到難燃效果，可使用摻混(blending)方式添加難燃劑或將纖維成品進行處理將難燃劑附著於纖維表面。然而，將聚酯高分子與難燃劑摻混雖然簡便，但常會有相容性不佳及難燃劑遷移(migration)造成難燃性下降的情形。另外，以難燃劑加工處理過的織物，在洗滌次數增加後，織物的難燃性則會下降。In order to achieve a flame retardant effect on the polyester polymer, a flame retardant may be added by using a blending method or the finished fiber may be treated to attach the flame retardant to the surface of the fiber. However, the blending of the polyester polymer and the flame retardant is simple, but there is often a case where the compatibility is poor and the flame retardant migration is caused by the migration of the flame retardant. Further, in the fabric treated with the flame retardant, the flame retardancy of the fabric is lowered after the number of washings is increased.
另一方面，可以共聚(copolymer)方式將難燃劑鍵結於高分子鏈上，此方法利用化學鍵結將難燃劑導入高分子鏈中，使其不受加工程序的影響而遷移至表面。先前文獻提出以具有雙醇結構的磷系化合物以共聚方式與萘二甲酸乙酯(bis(hydroxyethyl) naphthalate；BHEN)及萘二甲酸丁酯(bis(hydroxybutyl) naphthalate；BHBN)進行酯交換反應得到具有難燃特性的聚酯高分子。(Wang C.S.;Lin,C.H. "Synthesis and properties of phosphorus-containing PEN and PBN copolyesters" Polymer,1999,40,747.)。On the other hand, the flame retardant can be bonded to the polymer chain by a copolymerization method, and the method uses chemical bonding to introduce the flame retardant into the polymer chain to migrate to the surface without being affected by the processing procedure. The prior literature proposes that a phosphorus compound having a diol structure is copolymerized with a copolymer of bis(hydroxyethyl)naphthalate (BHEN) and bis(hydroxybutyl)phthalate (BHBN) to obtain a transesterification reaction. A polyester polymer having flame retardant properties. (Wang C.S.; Lin, C.H. "Synthesis and properties of phosphorus-containing PEN and PBN copolyesters" Polymer, 1999, 40, 747.).
因此，本發明之一態樣是在提供一種磷系二醇，可作為聚酯共聚物之組成單體，提供聚酯共聚物之難燃特性的。依照本發明之一或多個實施例，磷系二醇單體具有如下式(I)所示之結構：Accordingly, one aspect of the present invention provides a phosphorus diol which can be used as a constituent monomer of a polyester copolymer to provide flame retardant properties of the polyester copolymer. According to one or more embodiments of the present invention, the phosphorus diol monomer has a structure represented by the following formula (I):
其中，X為氫或甲基，R為氫原子、苯基、C1-C10烷基、C3-C10環烷基或鹵原子。Wherein X is hydrogen or a methyl group, and R is a hydrogen atom, a phenyl group, a C1-C10 alkyl group, a C3-C10 cycloalkyl group or a halogen atom.
本發明之一態樣是在提供一種製備如式(I)所示之磷系二醇單體的方法。包括利用一磷系化合物(a)、式(b)化合物與一鹼觸媒反應，其中鹼觸媒為CsF、KF、KI、CsCl、KCl、K2 CO3 、Na2 CO3 、KOH或NaOH，且鹼觸媒用量為磷系化合物(a)用量的0.1 wt%~10 wt%：One aspect of the present invention provides a method of preparing a phosphorus-based diol monomer as shown in the formula (I). The invention comprises the reaction of a compound of the phosphorus compound (a) and the compound of the formula (b) with a base catalyst, wherein the base catalyst is CsF, KF, KI, CsCl, KCl, K 2 CO 3 , Na 2 CO 3 , KOH or NaOH. And the amount of the base catalyst is 0.1 wt% to 10 wt% of the amount of the phosphorus compound (a):
本發明之一態樣是在提供一種以式(I)所示之磷系二醇為組成單體之難燃磷系聚酯共聚物。One aspect of the present invention provides a flame-retardant phosphorus-based polyester copolymer comprising a phosphorus-based diol represented by the formula (I) as a constituent monomer.
依照本發明之一實施例，難燃磷系聚酯共聚物具有如下式(II)所示之結構：According to an embodiment of the present invention, the flame-retardant phosphorus-based polyester copolymer has a structure represented by the following formula (II):
其中，X為氫或甲基，R為氫原子、苯基、C1-C10烷基、C3-C10環烷基或鹵原子，n=2-8，磷含量為共聚物的0.5-3.0重量百分比。Wherein X is hydrogen or methyl, R is a hydrogen atom, a phenyl group, a C1-C10 alkyl group, a C3-C10 cycloalkyl group or a halogen atom, n=2-8, and the phosphorus content is 0.5-3.0% by weight of the copolymer. .
依照本發明之另一實施例，難燃磷系聚酯共聚物具有如下式(III)所示之結構：According to another embodiment of the present invention, the flame-retardant phosphorus-based polyester copolymer has a structure represented by the following formula (III):
其中，X為氫或甲基，R為氫原子、苯基、C1-C10烷基、C3-C10環烷基或鹵原子，n=2-8，磷含量為共聚物的0.5-3.0重量百分比。Wherein X is hydrogen or methyl, R is a hydrogen atom, a phenyl group, a C1-C10 alkyl group, a C3-C10 cycloalkyl group or a halogen atom, n=2-8, and the phosphorus content is 0.5-3.0% by weight of the copolymer. .
根據上述，可知本發明實施例以磷原子取代傳統造成環境危害的鹵素原子合成難燃的磷系二醇單體，應用共聚方法導入聚酯高分子中，可在少量的難燃劑存在下即可有良好的阻燃效果，並維持難燃劑原有的特性，使難燃效果持久穩定。According to the above, it can be seen that the phosphorus atom in the embodiment of the present invention is substituted with a halogen atom which is conventionally caused by environmental hazards to synthesize a flame-retardant phosphorus-based diol monomer, and is introduced into the polyester polymer by a copolymerization method, which can be in the presence of a small amount of a flame retardant. It can have good flame retardant effect and maintain the original characteristics of the flame retardant, so that the flame retardant effect is lasting and stable.
本發明實施例之磷系二醇具有如式(I)所示之結構，可作為聚酯共聚物之組成單體，可與一醇酯單體進行酯交換，經由聚縮合反應形成磷系難燃聚酯共聚物。The phosphorus diol of the embodiment of the present invention has a structure represented by the formula (I), can be used as a constituent monomer of the polyester copolymer, can be transesterified with an alcohol ester monomer, and is difficult to form a phosphorus system by a polycondensation reaction. Burning polyester copolymer.
DMP-EC是以雙酚單體DMP與碳酸乙烯酯(ethylene carbonate,EC)在鹼性觸媒催化下反應而得。其中雙酚單體DMP如前述式(a)所示，R為甲基。磷系二醇單體DMP-EC合成步驟如下：在一附有溫度指示裝置之0.5升三頸反應器中，加入42.81克(0.1莫耳)的DMP、碳酸乙烯酯26.4克(0.3莫耳)，鹼觸媒為碳酸鉀30.34克(0.22莫耳)，溶劑為DMAc。升高反應溫度達120℃，將反應系統溫度維持在120℃並反應12小時後，滴入水中攪拌析出，抽氣過濾後之濾餅再用大量的去離子水洗滌。經過濾分離出之濾餅在110℃下真空烘乾即為產物(1)，產率為78%。產物之分子量以高解析質譜儀鑑定之。DMP-EC is obtained by reacting bisphenol monomer DMP with ethylene carbonate (EC) under basic catalyst catalysis. Wherein the bisphenol monomer DMP is represented by the above formula (a), and R is a methyl group. The phosphorus-based diol monomer DMP-EC was synthesized as follows: In a 0.5 liter three-neck reactor equipped with a temperature indicating device, 42.81 g (0.1 mol) of DMP and 26.4 g of ethylene carbonate (0.3 mol) were added. The base catalyst is 30.34 g (0.22 mol) of potassium carbonate, and the solvent is DMAc. The reaction temperature was raised to 120 ° C, the reaction system temperature was maintained at 120 ° C and reacted for 12 hours, and then dropped into water to be stirred and precipitated, and the filter cake after suction filtration was washed with a large amount of deionized water. The filter cake separated by filtration was vacuum dried at 110 ° C to give the product (1) in a yield of 78%. The molecular weight of the product was identified by high resolution mass spectrometry.
第1圖為產物(1)之1 H NMR圖譜。光譜分析的結果顯示，產物(1)為DMP-EC，分子式為C30 H29 O6 P，分子量為516.1698。Figure 1 is a 1 H NMR spectrum of the product (1). The results of the spectral analysis showed that the product (1) was DMP-EC having a molecular formula of C 30 H 29 O 6 P and a molecular weight of 516.1698.
根據本發明之一實施方式，難燃磷系聚酯共聚物可利用上述之磷系二醇單體與對苯二甲酸醇酯進行聚縮合反應而得，反應式如第2圖所示，可合成如式(II)所示之結構：According to one embodiment of the present invention, the flame-retardant phosphorus-based polyester copolymer can be obtained by a polycondensation reaction of the above-mentioned phosphorus-based diol monomer and terephthalic acid ester, and the reaction formula is as shown in FIG. Synthesize the structure shown in formula (II):
取21.77克(42.18 mmol)的產物(1)、90克(354 mmol)之對苯甲酸乙酯(bis(hydroxyethyl) terephthalate；BHET)、觸媒Ti(OBu)4 及醋酸鈷，置入500毫升三頸反應器中。將溫度升至270℃維持80分鐘後，將反應器內的壓力降至1-3 mmHg，並將溫度維持在約280℃進行聚縮合反應即可得到磷含量1.5 wt%之磷系難燃聚酯共聚物PET-1.5。21.77 g (42.18 mmol) of product (1), 90 g (354 mmol) of bis(hydroxyethyl) terephthalate; BHET, catalyst Ti(OBu) 4 and cobalt acetate, placed in 500 ml In a three-neck reactor. After the temperature was raised to 270 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg, and the temperature was maintained at about 280 ° C to carry out a polycondensation reaction to obtain a phosphorus-based flame retardant polymer having a phosphorus content of 1.5 wt%. Ester copolymer PET-1.5.
合成出的PET-1.5，其性質包括：極限黏度為0.58 dl/g，極限黏度可反應出高分子在溶液中的流體力學尺寸。利用1 H NMR積分面積所計算出來的實際磷含量為1.47 wt%，與預期值接近。利用動態機械測定儀(Dynamic Mechanical Analyzer；DMA)所測得玻璃轉移溫度為85℃，在UL-94垂直燃燒性質測試上則為V1等級。The synthesized PET-1.5 has properties including: the ultimate viscosity is 0.58 dl/g, and the ultimate viscosity can reflect the hydrodynamic size of the polymer in solution. The actual phosphorus content calculated using the 1 H NMR integrated area was 1.47 wt%, which was close to the expected value. The glass transition temperature was 85 ° C measured by a Dynamic Mechanical Analyzer (DMA) and V1 grade on the UL-94 vertical burning property test.
取27.69克(53.65 mmol)產物(1)、90g(354 mmol)之對苯甲酸乙酯、觸媒Ti(OBu)4 及醋酸鈷，置入500毫升三頸反應器中。將溫度升至270℃維持80分鐘後，將反應器內的壓力降至1-3 mmHg，並將溫度維持在約280℃進行聚縮合反應即可得到磷含量1.8 wt%之磷系難燃聚酯共聚物PET-1.8。27.69 g (53.65 mmol) of product (1), 90 g (354 mmol) of ethyl p-benzoate, catalyst Ti(OBu) 4 and cobalt acetate were placed in a 500 ml three-neck reactor. After the temperature was raised to 270 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg, and the temperature was maintained at about 280 ° C to carry out a polycondensation reaction to obtain a phosphorus-based flame retardant polymer having a phosphorus content of 1.8 wt%. Ester copolymer PET-1.8.
合成出的PET-1.5，其性質包括：極限黏度為0.56 dl/g，實際磷含量為1.76 wt%，與預期值接近。DMA所測得玻璃轉移溫度為90 ℃，在UL-94測試上則達到V0等級。The synthesized PET-1.5 has properties including an ultimate viscosity of 0.56 dl/g and an actual phosphorus content of 1.76 wt%, which is close to the expected value. The glass transition temperature measured by DMA was 90 °C, and the V0 rating was achieved on the UL-94 test.
取10.40克(20.15 mmol)產物(1)、90g(290 mmol)之對苯甲酸丁酯(bis(hydroxybutyl)terephthalate；BHBT)、觸媒Ti(OBu)4 及醋酸鈷，置入500毫升三頸反應器中。將溫度升至270℃維持80分鐘後，將反應器內的壓力降至1-3 mmHg，並將溫度維持在約260℃進行聚縮合反應即可得到磷含量1.8 wt%之磷系難燃聚酯共聚物PBT-1.8。Take 10.40 g (20.15 mmol) of product (1), 90 g (290 mmol) of butyl (hydroxybutyl) terephthalate (BHBT), catalyst Ti(OBu) 4 and cobalt acetate, and place 500 ml of three necks. In the reactor. After the temperature was raised to 270 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg, and the temperature was maintained at about 260 ° C to carry out a polycondensation reaction to obtain a phosphorus-based flame retardant polymer having a phosphorus content of 1.8 wt%. Ester copolymer PBT-1.8.
合成出的PBT-1.8，其性質包括：極限黏度為0.55 dl/g，實際磷含量為1.76 wt%，與預期值接近。DMA所測得玻璃轉移溫度為65 ℃，在UL-94測試上則達到V1等級。The synthesized PBT-1.8 has properties including an ultimate viscosity of 0.55 dl/g and an actual phosphorus content of 1.76 wt%, which is close to the expected value. The glass transfer temperature measured by DMA was 65 °C, and it reached the V1 level on the UL-94 test.
取14.63克(28.34 mmol)產物(1)、90g(290 mmol)之對苯甲酸丁酯、觸媒Ti(OBu)4 及醋酸鈷置入500毫升三頸反應器中。將溫度升至260℃維持80分鐘後，將反應器內的壓力降至1-3 mmHg，並將溫度維持在約260℃進行聚縮合反應即可得到磷含量2.3 wt%之磷系難燃聚酯共聚物PBT-2.3。14.63 g (28.34 mmol) of product (1), 90 g (290 mmol) of butylparaben, catalyst Ti(OBu) 4 and cobalt acetate were placed in a 500 ml three-neck reactor. After the temperature was raised to 260 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg, and the temperature was maintained at about 260 ° C to carry out a polycondensation reaction to obtain a phosphorus-based flame retardant polymer having a phosphorus content of 2.3 wt%. Ester copolymer PBT-2.3.
合成出的PBT-2.3，其性質包括：極限黏度為0.53 dl/g，實際磷含量為1.76 wt%，與估算值接近。利用DMA所測得玻璃轉移溫度為72 ℃，在UL-94測試上則可達到V0等級。The synthesized PBT-2.3 has properties including an ultimate viscosity of 0.53 dl/g and an actual phosphorus content of 1.76 wt%, which is close to the estimated value. The glass transition temperature measured by DMA was 72 °C, and the V0 rating was achieved on the UL-94 test.
根據本發明之另一實施方式，難燃磷系聚酯共聚物可利用上述之磷系二醇單體與對2,6-萘二甲酸醇酯進行聚縮合反應而得，反應式如第3圖所示，可合成如式(III)所示之結構：According to another embodiment of the present invention, the flame-retardant phosphorus-based polyester copolymer can be obtained by polycondensation reaction of the above-mentioned phosphorus-based diol monomer with 2,6-naphthalene dicarboxylate, and the reaction formula is as shown in the third As shown in the figure, a structure as shown in the formula (III) can be synthesized:
取6.69克(12.96 mmol)產物(1)、90g(250 mmol)之對-萘二甲酸醇酯(bis(hydroxyethyl)naphthalate；BHEN)、Ti(OBu)4 及醋酸鈷，置入500毫升三頸反應器中。將溫度升至260℃維持80分鐘後，將反應器內的壓力降至1-3 mmHg，並將溫度維持在約265℃進行聚縮合反應即可得到磷含量0.5 wt%之磷系難燃聚酯共聚物PBN-0.5。6.69 g (12.96 mmol) of product (1), 90 g (250 mmol) of bis(hydroxyethyl)naphthalate (BHEN), Ti(OBu) 4 and cobalt acetate, placed in a 500 ml three neck In the reactor. After the temperature was raised to 260 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg, and the temperature was maintained at about 265 ° C to carry out a polycondensation reaction to obtain a phosphorus-based flame retardant polymer having a phosphorus content of 0.5 wt%. Ester copolymer PBN-0.5.
合成出的PBN-0.5，其性質包括：極限黏度為0.56 dl/g，實際磷含量為0.48 wt%，與估算值接近。利用DMA所測得玻璃轉移溫度為126 ℃，在UL-94測試上則達到V0等級。The synthesized PBN-0.5 has properties including an ultimate viscosity of 0.56 dl/g and an actual phosphorus content of 0.48 wt%, which is close to the estimated value. The glass transition temperature measured by DMA was 126 °C, and the V0 rating was achieved on the UL-94 test.
取13.03克(12.96 mmol)產物(1)、90g(250 mmol)之對-萘二甲酸醇酯(bis(hydroxyethyl)naphthalate；BHEN)、Ti(OBu)4 及醋酸鈷，置入500毫升三頸反應器中。將溫度升至260℃維持80分鐘後，將反應器內的壓力降至1-3 mmHg，並將溫度維持在約265℃進行聚縮合反應即可得到磷含量1.0 wt%之磷系難燃聚酯共聚物PBN-1.0。Take 13.03 g (12.96 mmol) of product (1), 90 g (250 mmol) of bis(hydroxyethyl)naphthalate (BHEN), Ti(OBu) 4 and cobalt acetate, and place 500 ml of three necks. In the reactor. After the temperature was raised to 260 ° C for 80 minutes, the pressure in the reactor was lowered to 1-3 mmHg, and the temperature was maintained at about 265 ° C to carry out a polycondensation reaction to obtain a phosphorus-based flame retardant polymer having a phosphorus content of 1.0 wt%. Ester copolymer PBN-1.0.
其極限黏度為0.53 dl/g，利用1H NMR積分面積所計算出來的實際磷含量為0.98 wt%，與預估值接近。利用DMA所測得玻璃轉移溫度為92 ℃，在UL-94測試上則可達到V0等級。The ultimate viscosity is 0.53 dl/g, and the actual phosphorus content calculated using the 1H NMR integrated area is 0.98 wt%, which is close to the estimated value. The glass transition temperature measured by DMA was 92 °C, and the V0 rating was achieved on the UL-94 test.
合成出的PBN-0.5，其性質包括：極限黏度為0.53 dl/g，實際磷含量為0.98 wt%，與估算值接近。利用DMA所測得玻璃轉移溫度為126 ℃，在UL-94測試上則達到V0等級。The synthesized PBN-0.5 has properties including an ultimate viscosity of 0.53 dl/g and an actual phosphorus content of 0.98 wt%, which is close to the estimated value. The glass transition temperature measured by DMA was 126 °C, and the V0 rating was achieved on the UL-94 test.
由上述本發明實施方式可知，本發明實施例以磷原子取代傳統造成環境危害的鹵素原子合成難燃的磷系二醇單體，應用共聚方法導入聚酯高分子中，可在少量的難燃劑存在下即可有良好的阻燃效果，並維持難燃劑原有的特性，使難燃效果持久穩定。It can be seen from the above embodiments of the present invention that the phosphorus atom in the embodiment of the present invention is substituted with a halogen atom which is conventionally caused by environmental hazards, and is synthesized into a polyester polymer by a copolymerization method, and can be flame retarded in a small amount. In the presence of the agent, it has a good flame retardant effect, and maintains the original characteristics of the flame retardant, so that the flame retardant effect is lasting and stable.
本發明實施例之磷系難燃聚酯共聚物，可應用於難燃纖維、難燃織物、難燃不織物、難燃薄膜、難燃接著劑及難燃塑膠領域。The phosphorus-based flame retardant polyester copolymer of the embodiment of the invention can be applied to the fields of flame retardant fibers, flame retardant fabrics, flame retardant fabrics, flame retardant films, flame retardant adhesives and flame retardant plastics.
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.
無元件符號No component symbol
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下：The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.
第1圖為產物(1)之1 H NMR圖譜。Figure 1 is a 1 H NMR spectrum of the product (1).
第2圖為依照本發明一實施例之合成難燃磷系聚酯共聚物(II)的反應流程圖。Fig. 2 is a reaction flow chart for synthesizing a flame-retardant phosphorus-based polyester copolymer (II) according to an embodiment of the present invention.
第3圖為依照本發明一實施例之合成難燃磷系聚酯共聚物(III)的反應流程圖。Fig. 3 is a reaction flow chart for synthesizing a flame-retardant phosphorus-based polyester copolymer (III) according to an embodiment of the present invention.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127590A (en) * | 1975-10-14 | 1978-11-28 | Toyo Boseki Kabushiki Kaisha | Phosphorus-containing compounds |
| US4137201A (en) * | 1977-09-02 | 1979-01-30 | Eastman Kodak Company | Cyclic phosphonite stabilized cellulose ester compositions |
| TW438833B (en) * | 1999-04-16 | 2001-06-07 | Nat Science Council | Phosphorus containing flame retardant advanced epoxy resins, preparation and cured epoxy resins thereof |
| TW523526B (en) * | 2000-05-08 | 2003-03-11 | Chang Chun Plastics Co Ltd | Flame retardant resin and flame retardant composition containing the same |
| TW572954B (en) * | 2001-06-08 | 2004-01-21 | Chung Shan Inst Of Science | Phosphorus-containing compounds and their use in flame retardance |
| TW200637901A (en) * | 2005-04-20 | 2006-11-01 | Univ Nat Chunghsing | Flame-retardant curing agent containing phosphorus and its manufacturing method |
| TW201002732A (en) * | 2008-07-15 | 2010-01-16 | Univ Nat Chunghsing | Preparation of novel phosphorus-containing biphenols and their derivatives |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127590A (en) * | 1975-10-14 | 1978-11-28 | Toyo Boseki Kabushiki Kaisha | Phosphorus-containing compounds |
| US4137201A (en) * | 1977-09-02 | 1979-01-30 | Eastman Kodak Company | Cyclic phosphonite stabilized cellulose ester compositions |
| TW438833B (en) * | 1999-04-16 | 2001-06-07 | Nat Science Council | Phosphorus containing flame retardant advanced epoxy resins, preparation and cured epoxy resins thereof |
| TW523526B (en) * | 2000-05-08 | 2003-03-11 | Chang Chun Plastics Co Ltd | Flame retardant resin and flame retardant composition containing the same |
| TW572954B (en) * | 2001-06-08 | 2004-01-21 | Chung Shan Inst Of Science | Phosphorus-containing compounds and their use in flame retardance |
| TW200637901A (en) * | 2005-04-20 | 2006-11-01 | Univ Nat Chunghsing | Flame-retardant curing agent containing phosphorus and its manufacturing method |
| TW201002732A (en) * | 2008-07-15 | 2010-01-16 | Univ Nat Chunghsing | Preparation of novel phosphorus-containing biphenols and their derivatives |
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