CN112778362A - 一种松脂基内增塑pvc材料及其制备方法和应用 - Google Patents
一种松脂基内增塑pvc材料及其制备方法和应用 Download PDFInfo
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- CN112778362A CN112778362A CN202011577670.1A CN202011577670A CN112778362A CN 112778362 A CN112778362 A CN 112778362A CN 202011577670 A CN202011577670 A CN 202011577670A CN 112778362 A CN112778362 A CN 112778362A
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- acrolein
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 51
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 51
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 115
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 47
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 41
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- OGLDWXZKYODSOB-UHFFFAOYSA-N α-phellandrene Chemical compound CC(C)C1CC=C(C)C=C1 OGLDWXZKYODSOB-UHFFFAOYSA-N 0.000 claims description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 22
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 21
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- OGLDWXZKYODSOB-SNVBAGLBSA-N alpha-phellandrene Natural products CC(C)[C@H]1CC=C(C)C=C1 OGLDWXZKYODSOB-SNVBAGLBSA-N 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000013557 residual solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000005074 zinc chloride Nutrition 0.000 claims description 11
- 239000011592 zinc chloride Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- -1 phosphorus ester Chemical class 0.000 claims description 10
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- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
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- HENMSNJYDGNBMU-UHFFFAOYSA-M calcium;zinc;octadecanoate Chemical compound [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O HENMSNJYDGNBMU-UHFFFAOYSA-M 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 3
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 3
- RRJHOMPUEYYASJ-UHFFFAOYSA-N ditert-butyl hydrogen phosphite Chemical compound CC(C)(C)OP(O)OC(C)(C)C RRJHOMPUEYYASJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- RQKYHDHLEMEVDR-UHFFFAOYSA-N oxo-bis(phenylmethoxy)phosphanium Chemical compound C=1C=CC=CC=1CO[P+](=O)OCC1=CC=CC=C1 RQKYHDHLEMEVDR-UHFFFAOYSA-N 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000010617 anise oil Substances 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
- C07F9/4009—Esters containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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- C07F9/40—Esters thereof
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- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C08K5/00—Use of organic ingredients
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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Abstract
本发明属于塑料添加剂领域,具体涉及一种松脂基内增塑PVC材料及其制备方法和应用。本发明将带有共轭双键的松脂基衍生物与丙烯醛经Diels‑alder反应得松脂基丙烯醛加成物;然后将松脂基丙烯醛加成物与多元胺、亚磷酸二乙酯经Mannich缩合反应可得到一种松脂基曼尼希碱;最后将松脂基曼尼希碱与PVC经取代反应得到松脂基内增塑PVC材料。制备的内增塑PVC材料玻璃化转变温度低至28℃,并且具有优异的耐溶剂抽出性能和力学性能。
Description
技术领域
本发明属于塑料添加剂领域,具体涉及一种松脂基内增塑PVC材料及其制备方法和应用。
背景技术
聚氯乙烯(PVC)是世界五大通用树脂之一,被广泛应用于建筑、电力、公用事业等领域。PVC应用如此广泛要归功于不同助剂的使用,尤其是增塑剂。增塑剂在PVC加工成型中促使其易加工,赋予制品柔软性。目前全球增塑剂品种多达200余种,其中传统的石油基邻苯二甲酸酯类增塑剂因其价格低廉和赋予PVC制品良好的机械性能在过去几十年一直是消费者的首选增塑剂。但该类增塑剂因易迁移到周围环境中并带来潜在生殖毒性及环境威胁而被禁止在电子、食品包装、日用品及医药卫生等领域使用。随着全球环保法规的日趋严格,研究和开发新型无毒绿色增塑剂以及高性能、耐油、耐抽提、耐迁移等新型增塑剂已成为当务之急。
增塑剂在配料过程中加入,一般不与聚合物起化学反应,且当制品受到热辐射或者接触到抽出能力较强的酸碱溶液时,会被抽出或者自行迁移,制品自身物理化学性质也会随之发生改变,影响制品的性能和使用寿命。通过取代反应将其接枝到PVC中来改善PVC的增塑性,解决PVC制品中增塑剂易迁移引起的机械性能缺失和人体潜在危害等问题,是一种十分有效的方法。
我国松脂资源丰富,其中双江地区云南松松脂中含有高达30.3%的β-蒎烯。工业上β-蒎烯经热异构化可以制备纯度约为80%的月桂烯(即7-甲基-3–亚甲基-1,6辛二烯),精馏后可将纯度提升至99%。水芹烯是存在于桉树油、大茴香油、小茴香油、肉桂叶油、松节油等多种挥发油中的单环萜类化合物,包括α-水芹烯和β-水芹烯两种同分异构体。此外,α-水芹烯在桧属和松属植物中含量较多,在水芹和灌木柴胡中也有存在,中国某些松树如湿地松、云南松松脂单萜中β-水芹烯含量可高达10%。月桂烯和α-水芹烯中的不饱和的碳碳双键,易发生多种化学反应,如:Diels-Alder反应、还原反应和氧化反应等。因此,通过与丙烯醛经Diels-alder反应得松脂基丙烯醛加成物;然后将松脂基丙烯醛加成物与多元胺、亚磷酸二乙酯经Mannich缩合反应可得到一种松脂基曼尼希碱;最后将松脂基曼尼希碱与PVC经取代反应得到松脂基PVC材料,可达到内增塑PVC的同时避免增塑剂的迁移。
发明内容
本发明为应对市场上现有的石油源增塑剂产品存在的易迁移到周围环境中并带来潜在生殖毒性及环境威胁等问题,提供了一种松脂基内增塑PVC材料及其制备方法和应用。
本发明采用的技术方案如下:
一种松脂基内增塑PVC材料,其特征在于,该松脂基内增塑PVC材料结构通式为:
上述松脂基内增塑PVC材料,其特征在于,R1为C1-C6的直链、C1-C6支链烷基或C1-C6的环烷基,优选为C1-C6的支链烷基和含双键的C1-C6的环烷基,更优选为含双键的C1-C6环烷基。
上述松脂基内增塑PVC材料,其特征在于,R2为含C2-C16直链烷基的磷酯、C2-C16支链烷基的磷酯或对称苯环的磷酯,优选为C2-C6的支链烷基的磷酯,更优选为含C4烷基的磷酯。
上述松脂基内增塑PVC材料的制备方法,步骤为:
第一步:将松脂衍生物A和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至40~55℃后,滴加丙烯醛(松脂衍生物A和丙烯醛摩尔比为1:1.1)。然后,将混合物加热至60℃并保持反应6小时。反应结束后用质量分数为10%氯化钠溶液和5%碳酸氢钠溶液洗涤、无水硫酸镁干燥、旋转蒸发器除去多余的丙烯醛并回收,最终得到淡黄色液体松脂基丙烯醛加成物。
第二步:将二乙烯三胺加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,将月桂烯丙烯醛加成物逐渐添加到溶液中,二乙烯三胺和松脂基丙烯醛加成物摩尔比为1:1。将混合物在20℃搅拌2h,然后升至90℃。此后,反应物B在连续搅拌下缓慢滴入容器中,二乙烯三胺和反应物B摩尔比为1:1,然后在90℃下反应4h;之后,经除去水分得到一种淡黄色的黏液状产物即松脂基曼尼希碱。
第三步:将PVC和松脂基曼尼希碱按质量比为5:1~4溶解于DMF中,得到澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物溶解于THF中。最后,将溶液倒入玻璃皿中,在室温下干燥以蒸发残余溶剂,自塑化PVC膜从培养皿中分离出来,在真空烘箱中60℃下进一步干燥得到松脂基内增塑PVC材料。
上述松脂衍生物A为月桂烯、α-水芹烯或双戊烯中的一种。
上述反应物B为亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二丁酯、亚磷酸二叔丁酯、亚磷酸二苯酯、亚磷酸二苄酯、亚磷酸二异辛基酯中的一种。
上述的内增塑PVC在制备PVC制品中的应用。
上述的内增塑PVC在制备PVC制品中的应用,其特征在于,PVC制品按质量份计,100份松脂基内增塑PVC,0~3份硬脂酸钙锌复合热稳定剂。
有益效果:①本发明制得的松脂基内增塑PVC材料中的烷基、六元脂环、多元磷酯等结构可改善PVC与PVC间的相容性,提高材料的增塑效果、耐迁移性和耐挥发性。②本发明原料来源丰富、合成工艺简单,生产成本低。③选用松脂的衍生物—月桂烯、双戊烯或水芹烯为原料制备高效内增塑PVC材料,有利于提高绿色可再生资源的利用,促进绿色环保可持续发展。
附图说明
图1为月桂烯基内增塑PVC红外光谱图。
具体实施方式
文中未涉及部分均与现有技术相同或可采用现有技术加以实现。下述便是本发明的优选实施例,但本发明也不局限于以下仅有的实施例,在实施例上稍做改进也将视为本发明的保护范围。
实施例1
(1)将月桂烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(月桂烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到月桂烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加月桂烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二乙酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得月桂烯基曼尼希碱;
(3)将7g PVC和1.4g的月桂烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物共5g溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到月桂烯基内增塑PVC材料。
实施例2
(1)α-水芹烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(α-水芹烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到水芹烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加水芹烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二甲酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得水芹烯基曼尼希碱;
(3)将7g PVC和4.2g的水芹烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物共5g溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到水芹烯基内增塑PVC材料。
实施例3
(1)双戊烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(双戊烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到双戊烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加双戊烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二丁酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得双戊烯基曼尼希碱;
(3)将7g PVC和2.8g的双戊烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物共5g溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到双戊烯基内增塑PVC材料。
实施例4
(1)α-水芹烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(α-水芹烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到α-水芹烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加水芹烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二叔丁酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得水芹烯基曼尼希碱;
(3)将7g PVC和4.2g的水芹烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物共5g溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到水芹烯基内增塑PVC材料。
实施例5
(1)月桂烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(月桂烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到月桂烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加月桂烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二苯酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得月桂烯基曼尼希碱;
(3)将7g PVC和1.4g的月桂烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物共5g溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到月桂烯基内增塑PVC材料。
实施例6
(1)双戊烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(双戊烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到双戊烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加双戊烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二苄酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得双戊烯基曼尼希碱;
(3)将7g PVC和1.4g的双戊烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物共5g溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到双戊烯基内增塑PVC材料。
实施例7
(1)将α-水芹烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(将水芹烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到将水芹烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加水芹烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二异辛基酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得水芹烯基曼尼希碱;
(3)将7g PVC和4.2g的水芹烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物共5g溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到水芹烯基内增塑PVC材料。
实施例8
(1)将α-水芹烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(将水芹烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到将水芹烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加水芹烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二乙酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得水芹烯基曼尼希碱;
(3)将7g PVC和4.2g的水芹烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将上述产物共5g溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到水芹烯基内增塑PVC材料。
实施例9
(1)将月桂烯和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至55℃后,滴加丙烯醛(将月桂烯和丙烯醛摩尔比为1:1.1),使温度保持在60℃下反应6h。反应结束后,经10%氯化钠溶液(质量分数)和5%碳酸氢钠溶液(质量分数)洗涤、无水硫酸镁干燥、旋转蒸发除去多余的丙烯醛,得到将月桂烯丙烯醛加成物。
(2)将二乙烯三胺(0.1mol)加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,逐滴添加月桂烯丙烯醛加成物(0.1mol)到烧瓶中。将混合物在20℃搅拌2h,然后升至90℃后缓慢滴加亚磷酸二乙酯(0.1mol),90℃下反应4h。所得产物蒸馏除去水分得月桂烯基曼尼希碱;
(3)将7g PVC和1.4g的月桂烯基曼尼希碱溶解于80mL DMF中1h,以制备澄清的淡黄色溶液。然后用甲醇多次洗涤所得产物,并在干燥箱中于60℃下干燥。将5g上述产物、0.01g硬脂酸钙锌复合热稳定剂。溶解于60mL THF中。最后,将溶液倒入玻璃皿中,在室温下干燥2天以蒸发残余溶剂。自塑化PVC膜从培养皿中分离出来,在烘箱中60℃下进一步干燥过夜,得到月桂烯基内增塑PVC材料。
实施例中所采用的松脂基内增塑PVC材料的红外光谱谱图,以月桂烯基内增塑PVC材料为例见附图1。图1中月桂烯基内增塑PVC材料在1640cm-1出现双键的特征吸收峰、1725cm-1出现醛基的特征吸收峰、1331cm-1出现六原子环的特征吸收峰,且2977、2912、2837、1668、1026、957和690cm-1处的峰分别归属于C-H(sp)、C-H(sp3)、C-H(sp2)、N-H拉伸振动、C-N、P-O和N-H摇摆振动。显然,随着MMA置换PVC中氯原子的增加,这些峰变得更强。另外,PVC的C-Cl伸缩振动峰在627cm-1处逐渐变弱,说明氯原子被取代,且在1594cm-1(月桂烯的共轭双键)、3086和1796cm-1(末端乙烯基)处无特征吸收峰,表明月桂烯基内增塑PVC材料制备成功。
对实施例中所制备的松脂基内增塑PVC材料(厚度0.41cm)分别通过差示扫描量热仪和微机控制电子万能试验机测试其玻璃化转变温度和力学性能,结果见表1。分别将一定质量的PVC材料置于正己烷溶剂中,50℃下浸入2小时后烘干称重,获得质量损失百分比,以评价松脂基内增塑PVC材料的耐溶剂抽出性能,结果见表1。结果显示所制备的松脂基内增塑PVC材料玻璃化转变温度可低至28℃,且具有优异的耐溶剂抽出性能和力学性能。
表1实验组1组成
PVC材料的拉伸性能参照GB/T 1040.1-2006《塑料拉伸试验方法》,采用CMT4000型微机控制电子万能试验机(深圳新三思),测定材料的拉伸性能和弯曲性能,拉伸测试速度为50mm/min,测试温度均为25℃。
Claims (9)
2.如权利要求1所述的一种松脂基内增塑PVC材料,其特征在于,R1为C1-C6的直链、C1-C6支链烷基或C1-C6的环烷基;R2为含C2-C16直链烷基的磷酯、C2-C16支链烷基的磷酯或对称苯环的磷酯。
3.如权利要求2所述的一种松脂基内增塑PVC材料,其特征在于,R1为C1-C6的支链烷基和含双键的C1-C6的环烷基;R2为C2-C6的支链烷基的磷酯。
4.如权利要求2或3所述的一种松脂基内增塑PVC材料,其特征在于,R1为含双键的C1-C6环烷基;R2为含C4烷基的磷酯。
5.如权利要求1所述的一种松脂基内增塑PVC材料的制备方法,其特征在于,
第一步:将松脂衍生物A和氯化锌按摩尔比1:0.25加入到反应容器中,温度升至40~55℃后,滴加丙烯醛,松脂衍生物A和丙烯醛摩尔比为1:1.1;然后,将混合物加热至60℃并保持反应6小时,反应结束后用氯化钠溶液和碳酸氢钠溶液洗涤、无水硫酸镁干燥、旋转蒸发器除去多余的丙烯醛并回收,最终得到淡黄色液体松脂基丙烯醛加成物;
第二步:将二乙烯三胺加入装有回流冷凝器、滴液漏斗、温度计和搅拌器的烧瓶中,将月桂烯丙烯醛加成物逐渐添加到溶液中,二乙烯三胺和松脂基丙烯醛加成物摩尔比为1:1;将混合物在20℃搅拌2h,然后升至90℃;此后,反应物B在连续搅拌下缓慢滴入容器中,二乙烯三胺和反应物B摩尔比为1:1,然后在90℃下反应4h;之后,经除去水分得到一种淡黄色的黏液状产物即松脂基曼尼希碱;
第三步:将PVC和松脂基曼尼希碱按质量比为5:1~4溶解于DMF中,得到澄清的淡黄色溶液;然后用甲醇多次洗涤所得产物,并在干燥箱中干燥;将上述产物溶解于THF中;最后,将溶液倒入玻璃皿中,在室温下干燥以蒸发残余溶剂,自塑化PVC膜从培养皿中分离出来,在真空烘箱中干燥得到松脂基内增塑PVC材料。
6.如权利要求5所述的一种松脂基内增塑PVC材料的制备方法,其特征在于,第一步中,松脂衍生物A为月桂烯、α-水芹烯或双戊烯中的一种;氯化钠溶液和碳酸氢钠溶液的质量分数分别为10%和5%。
7.如权利要求5所述的一种松脂基内增塑PVC材料的制备方法,其特征在于,第二步中,反应物B为亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二丁酯、亚磷酸二叔丁酯、亚磷酸二苯酯、亚磷酸二苄酯、亚磷酸二异辛基酯中的一种。
8.如权利要求5所述的一种松脂基内增塑PVC材料的制备方法,其特征在于,第三步中,干燥箱和真空烘箱的温度均为60℃。
9.如权利要求1所述的一种松脂基内增塑PVC材料在制备PVC制品中的应用,其特征在于,PVC制品按质量份计,100份松脂基内增塑PVC,0~3份硬脂酸钙锌复合热稳定剂。
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