Application research of low volatile environmental plasticizer di（2⁃propylheptane） terephthalate

doi:10.19491/j.issn.1001-9278.2022.01.020

Abstract

Abstract:

Using terephthalic acid and 2?propylheptanol as raw materials， isopropyl titanate as a catalyst， bis（2?propylheptyl） terephthalate （DPHTP） were obtained by esterification. And using DPHTP as a plasticizer to prepare polyvinyl chloride （PVC） flexible film， and compare the application performance with the common DOP and DOTP on the market. The molecular structure of plasticizer was verified by FTIR and ¹H?NMR. The differences in mechanical properties of DPHTP， DOP and DOTP plasticized PVC films are compared by TGA， tensile test， migration resistance test and volatility resistance test. The results show that， compared with DOP and DOTP， DPHTP plasticized film has better thermal stability and higher volume resistivity. Respectively， the volume resistivity of DPHTP plasticized film is 6.5×10⁹， the 5 % thermal weight loss temperature is 272 ℃， the heating loss of DPHTP is 0.031 90 %. The conclusion shows that DPHTP has lower volatility and can endow PVC materials with excellent electrical insulation properties， and it was predicted to have broad development prospects in packaging materials and wire and cable industries.

Key words: di（2?propylheptyl） terephthalate, polyvinyl chloride, environmentally friendly plasticizer, plastic additives

CLC Number:

TQ325.3

FENG Shan, JIANG Pingping, ZHANG Pingbo, ZHANG Zheming, ZHANG Kai, GU Qian. Application research of low volatile environmental plasticizer di（2⁃propylheptane） terephthalate[J]. China Plastics, 2022, 36(1): 135-141.

Figures/Tables 11

References 21

1	DOMINGUEZ C I， FERRJ J M， CARDONA， S C， et al. Dual plasticizer/thermal stabilizer effect of epoxy⁃ dized chia seed oil （Salvia hispanica L.） to improve ductility and thermal properties of poly（lactic acid）［J］. Polymers （Basel）， 2021， 13 （8）： 1 283.
2	JIA P， ZHANG M， HU L， FENG G， et al. Synthesis and application of environmental castor oil based polyol ester plasticizers for poly（vinyl chloride）［J］. ACS Sustainable Chemistry & Engineering， 2015， 3 （9）： 2 187⁃2 193.
3	HAO Y， TIAN A， ZHU J， et al.Synthesis and evaluation of bio⁃based plasticizers from 5⁃hydroxymethyl⁃2⁃furancarboxylic acid for poly（vinyl chloride）［J］. Industrial & Engineering Chemistry Research， 2020， 59 （40）： 18 290⁃18 297.
4	SONG F， HUANG C， ZHU X， et al. Synthesis and application of an environmental epoxy plasticizer with phthalate‐like structure based on tung oil and cardanol for poly（vinyl chloride）［J］. Journal of Applied Polymer Science， 2021， 138 （33）： 50 809.
5	JIA P， HU L， YANG X， et al. Internally plasticized PVC materials via covalent attachment of aminated tung oil methyl ester［J］. RSC Advances， 2017， 7 （48）： 30 101⁃30 108.
6	ZHANG H， ZHU F， FU Q， et al. Mechanical properties of renewable plasticizer based on ricinoleic acid for PVC［J］. Polymer Testing， 2019， 76： 199⁃206.
7	LIU D， SHEN Y， WAI P T， et al. An efficient plasticizer based on waste cooking oil： Structure and application［J］. Journal of Applied Polymer Science， 2020， 138 （13）： 50 128.
8	MA Y， SONG F， KONG Q， et al. Preparation and performance of bio⁃based polyol ester from one⁃pot synth⁃esis of castor oil as nontoxic poly （vinyl chloride） plasticizer［J］. Journal of Polymers and the Environment， 2020， 28 （8）： 2 101⁃2 107.
9	蒋平平，高巍，张萍波，等.对苯二甲酸二（2⁃乙基）已酯（DOTP）制备技术路线及产业化应用［J］.塑料助剂， 2019（5）： 9⁃16.
	JIANG P P， GAO W， ZHANG P B， et al. Di（2⁃ethyl）hexyl terephthalate（DOTP）：technical routes of preparation and its industrial application［J］. Plastics Additives， 2019（5）： 9⁃16.
10	MUKHERJEE S， GHOSH M. Performance Evaluation and biodegradation study of polyvinyl chloride films with castor oil‐based plasticizer［J］. Journal of the American Oil Chemists' Society， 2019， 97 （2）： 187⁃199.
11	LIU D， SHEN Y， JIANG P， et al. An efficient cold⁃resistant strategy： Synthesis and application of green col⁃ d⁃resistant bio⁃based plasticizer for poly（vinyl chloride）［J］. European Polymer Journal， 2021， 142.
12	ZIA A I， SYAIFUDIN A R M， MUKHOPADHYAY S C， et al. Electrochemical impedance spectroscopy based MEMS sensors for phthalates detection in water and juices［J］. Journal of Physics： Conference Series， 2013， 439： 012026.
13	李金平，唐蓉，徐国刚，等.浅谈食品中塑化剂的危害与应对措施［J］.中国新技术新产品， 2013（7）： 181⁃190.
	LI J P， TANG R， XU G G， et al. Discussion on the harm of the plasticizer in food and countermeasures［J］. New Technology & New Products of China， 2013（7）： 181⁃190.
14	李博，谢海波，王彦文，等.生物基增塑剂的研究进展［J］.广东化工， 2021， 48（5）： 59⁃61.
	LI B， XIE H B， WANG Y W， et al. Research progress of biological plasticizers［J］. Guangdong Chemical Industry， 2021，48（5）： 59⁃61.
15	CHEN J， LIU Z， WANG K， et al. Epoxidized castor oil‐based diglycidyl‐phthalate plasticizer： synthesis and thermal stabilizing effects on poly（vinyl chloride）［J］. Journal of Applied Polymer Science， 2018， 136 （9）： 47 142.
16	XIE Y， YU B， ZHANG Y， et al. Antibacterial plasticizers based on bio⁃based engineering elastomers for medical PVC： synthesis， characterization and properties［J］. Polymer Chemistry， 2021， 12 （8）： 1 114⁃1 124.
17	张玉环，雷亚楠，鲁皓，等.食品中邻苯二甲酸酯类塑化剂的检测技术研究进展［J］.食品安全质量检测学报， 2021， 12（1）： 202⁃209.
	ZHANG Y H， LEI Y N， LU H， et al. Research progress on the detection of phthalic acid ester plasticizers in food［J］. Journal of Food Safety & Quality， 2021， 12（1）： 202⁃209.
18	JIA P， MA Y， XIA H， et al. Clean synthesis of epoxidized tung oil derivatives via phase transfer catalyst and thiolene reaction： a detailed study［J］. ACS Sustainable Chemistry & Engineering， 2018， 6 （11）： 13 983⁃13 994.
19	LI M， LI S， XIA J， DING C. et al. Tung oil based plasticizer and auxiliary stabilizer for poly（vinyl chloride）［J］. Materials & Design， 2017， 122： 366⁃375.
20	WANG Y， NIE X， FANG G， et al. Synthesis and application of a novel thermostable epoxy plasticizer based on levulinic acid for poly（vinyl chloride）［J］. Journal of Applied Polymer Science， 2020， 137 （36）： 49 066.
21	ZHANG Z， JIANG P， LIU D， etal. Research progress of novel bio⁃based plasticizers and their applications in poly（vinyl chloride）［J］. Journal of Materials Science， 2021， 56 （17）： 10 155⁃10 182.

物质名称	保留时间/min	开始时间/min	结束时间/min	峰面积	检测处峰面积与所有峰面积之和的比值/%	峰高	检测处峰高与所有峰高之和的比值/%
2?PH	6.176	6.158	6.200	6.12×10⁵	0.21	452 201	0.54
DPHTP	18.165	18.125	18.180	2.17×10⁷	7.31	12 368 747	14.81
DPHTP	18.196	18.178	18.245	2.26×10⁷	7.59	12 547 661	15.02
DPHTP	18.524	18.408	18.633	2.52×10⁸	84.89	58 144 917	69.63

物质名称	保留时间/min	开始时间/min	结束时间/min	峰面积	检测处峰面积与所有峰面积之和的比值/%	峰高	检测处峰高与所有峰高之和的比值/%
2?PH	6.176	6.158	6.200	6.12×10⁵	0.21	452 201	0.54
DPHTP	18.165	18.125	18.180	2.17×10⁷	7.31	12 368 747	14.81
DPHTP	18.196	18.178	18.245	2.26×10⁷	7.59	12 547 661	15.02
DPHTP	18.524	18.408	18.633	2.52×10⁸	84.89	58 144 917	69.63

PVC样品	断裂伸长率/%	最大拉伸强度/MPa	200 %处表观模量/MPa	400 %处表观模量/MPa	弹性模量/MPa	肖氏硬度/HA
DOTP?60	671.3±2.1	23.9±0.7	5.1±0.2	3.9±0.1	5.9±0.2	89±0.7
DPHTP?60	743.8±7.9	24.2±0.1	5.5±0.2	4.0±0.2	5.5±0.2	94±1.0
DOP?60	679.6±4.9	21.3±0.8	4.2±0.1	3.3±0.2	4.9±0.2	86±0.9

PVC样品	断裂伸长率/%	最大拉伸强度/MPa	200 %处表观模量/MPa	400 %处表观模量/MPa	弹性模量/MPa	肖氏硬度/HA
DOTP?60	671.3±2.1	23.9±0.7	5.1±0.2	3.9±0.1	5.9±0.2	89±0.7
DPHTP?60	743.8±7.9	24.2±0.1	5.5±0.2	4.0±0.2	5.5±0.2	94±1.0
DOP?60	679.6±4.9	21.3±0.8	4.2±0.1	3.3±0.2	4.9±0.2	86±0.9

增塑剂	加热减量/%	PVC试样	5%失重温度/℃
DOP	0.242 60	DOP?60	252
DOTP	0.083 12	DOTP?60	262
DPHTP	0.031 90	DPHTP?60	272