CN1004491B - 硬聚氯乙烯型件的粘合剂 - Google Patents
硬聚氯乙烯型件的粘合剂 Download PDFInfo
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Abstract
一种粘合硬聚氯乙烯型件的组合物,是一种PVC溶液,含有环状PVC溶剂的液体溶剂混合物,PVC固体含量为10-30%(重量);溶剂混合物中的环状PVC溶剂含量不超过50%(重量,以粘合剂重量为基数计);以K值范围为45至52的PVC值与K值为58±1的PVC相混合,优先选择方案是,K值为58±1的PVC,用量为40至85重量%(以PVC总重量计),优先选择45至60重量%;K值为45-52的PVC,用量为60至15重量%(以PVC总重量计),优先选择55至40重量%。
Description
本发明涉及一种用于硬聚氯乙烯(PVC)型件的改良粘合剂,尤其是在应为诱导腐蚀显著降低的趋势下甚至在高要求的应用中都能满足当今对储存稳定性、标准适合性、蠕变强度和缝隙填充能力各项要求的材料。
对于粘合硬聚氯乙烯型件,如聚氯乙烯高压管,通常所用的粘合剂含有溶于适当的聚氯乙烯溶剂或溶剂体系的粉末状聚氯乙烯。通过选择合适的溶剂体系来调节这些粘合体系的加工性能,如加工时间和膨胀性能。
粘合原理是基于溶剂的膨胀、溶解和扩散能力。溶剂扩散到基础材料中,使其溶胀并与溶液中的PVC结合,当把粘合物与基础材料挤压在一起时就能实现联结。
溶剂通过一段没有精确地限定时间的解吸后便可得到均匀的联结。
系统研究表明,这种粘合材料中含有的溶剂由于共溶解、蒸发及增塑性能而对可能产生的结构损伤有不同的影响,此情况对高压力型件变得特别重要,如四通接头,其任何情况下的机械负荷,都有剩余的粘合剂经筒内部转移至筒芯的粘合剂附加积累。
本发明的改良硬聚氯乙烯粘合剂的技术构思出发点是认为,某些已知的好的PVC溶剂组成是造成上述不希望有的结构损伤的原因。申请人的试验表明,具有环状结构的聚氯乙烯溶剂、即环己酮、四氢呋喃(在一定程度上)可造成损伤,特别是应力诱导腐蚀。四氢呋喃和环己酮二者均为PVC的好溶剂(参看“塑料70”(1980),313至318页)。
这种溶剂用于此类粘合剂组合物是好的,或者为满足按照粘合剂组合物或硬PVC最后形成的联结的各种要求来说都是必需的。
这样,这些粘合剂强度就必须满足许多标准要求-其中有西德工业标准(DIN)16970,KIWA No.55,英国标准化协会(BSI)4346,美国材料检验学会(ASTM)2564和日本自来水厂协会标准(JWWAS)101。这些要求决定于粘合剂中所加聚氯乙烯成分的分子量和分子量分布情况的选择,例如西德工业标准16970的所谓60℃试验要求用于粘合材料的聚氯乙烯原料要有足够的热稳定性。这种热稳定性依赖于前面提到的材料参数。
按照申请人的试验,对于这里涉及的聚氯乙烯粘合材料,在粘合剂中所加聚氯乙烯的性能和经济上的最适度,其K值为58±1。鉴于该聚氯乙烯原料的溶解行为、存放稳定、适合标准、可填充缝隙和抗蠕变性,粘合剂要求上述环状PVC溶剂有相对高的百分组成。通过将K值降低到所给界限以下以用非环组分代替溶剂组成的所有试图均未成功,因为这样粘合剂组合物在上述4个标准中,至少有一项不能或不再满足。
本发明基于观察,发现将不同K值的PVC类型结合,可得到符合标准的粘合剂配方,并且存放稳定,能填充缝隙和防止蠕变。同时,与现有实际应用的已知粘合剂组合物相比,由于溶剂混合物中上述环状PVC溶剂量的限制,符合有效减少应力龟裂的趋向。因此,本发明涉及硬PVC型件粘合的组合物是基于含环状PVC溶剂混合物的PVC溶液,其PVC固体含量约为10至30%(重量)。该新粘合剂组合物的特征是含有K值为58±1的溶解PVC与K值范围在45至52之间的溶解PVC溶液(其溶剂混合物中的环状PVC溶剂含量不超过总粘合剂重量的50%)相混合。在一最佳实施方案中该新粘合剂组合物含下列两种以溶液互相混合的PVC类型:
K值为58±1的PVC和K值约为49至50的PVC。
在另一最佳实施方案中,K值为58±1的PVC成分约为溶解的两种PVC类型重量总的40至85%,特别是45至60%,而K值较低的PVC相应为60至15%,在特别的最佳实施方案中为55至40%,推荐使用的是将同等重量的两类PVC溶于溶剂混合物。
本发明的一个显著的特征是,不需要放弃使用已知的环状结构的聚氯乙烯好溶剂,而只需限制其在溶剂混合物中的含量,即可满足降低应力诱导腐蚀的要求。
因此,在本发明的一个最佳实施方案中,PVC溶剂混合物中所含的环状溶剂(特别是四氢呋喃和/或环己酮)的量为粘合剂总量的约30-50%,特别是约35-45%。
本发明的粘合剂组合物液相的其余部分为非环状PVC溶剂,其中重要的是非环酮,首先是丁酮更为重要。此外为其它非环状PVC溶剂,其量一般很小,在这种情况下,使用有限量的二甲基甲酰胺可能又有特别的意义。
本发明的特别优先选择的粘合剂组合物含有约20%(重量)的溶解的上述种类的PVC成分、约40至50%(重量)的四氢呋喃和环己酮,最好是以约1∶1至2∶1的比例混合;其余的为非环状PVC溶剂,其中丁酮为25至35%(重量),其余为二甲基甲酰胺。这里的重量百分数均以粘合剂组合物总重为基数计算。
本发明的粘合剂证实了申请人所发现的这一事实,即由应力诱导腐蚀造成的不希望的损害按下列所选的粘合剂体系的溶剂而递增:二氯甲烷/二甲基甲酰胺/丁酮/四氢呋喃/环己酮。以两种方法测定比较数值,以估价引起应力龟裂时溶剂的作用:
1、在溶剂发挥作用后用冲击试验测定脆化点
标准是解吸1000小时后,作为温度函数的断裂率为50%。
PVC -52℃(空白试验)
二氯乙烷 -38℃
二甲基甲酰胺 -28℃
丁酮 -21℃
四氢呋喃 +12℃
环己酮 +22℃
2、溶剂于-5℃解吸168小时后,再于+20℃解吸1小时,测定管截面最大抗压强度
标准:直径压缩30%时的折断率或龟裂率。
PVC 0%
二氯乙烷 0%
丁酮 20% 裂缝
四氢呋喃 100% 裂缝
在下面1至9的配方中,1号是比较例,是一标准的市售的这种类型的PVC粘合剂,含最适PVC组分,K-值为58,溶解形式。2至6号配方仍为比较例,说明用与本发明的构思不同的其它途径降低应力龟裂水平的结果。从2至6的比较可以看出,没有一例能满足所有要求(包括减少应力龟裂的危险性)。
例7、8和例9欲说明本发明的思想,在每例中都达到了将所有希望的性质结合在一起的目的。
试验部分
比较例1(现有技术)
PVC K-值58 20% 附注
四氢呋喃 50% 正:符合标准、
环己酮 20% 抗蠕变、
二甲基甲酰胺 5% 可填充缝隙
丁酮 5% 负:粘接材料过多时
有应力龟裂危险
减少应力龟裂的比较试验(2至6号)
比较例2
K-值为56的PVC 20% 附注
四氢呋喃 40% 正:降低了应力龟裂
环己酮 10% 危险
二甲基甲酰胺 5% 负:不符合标准,
丁酮 25% 热稳定性低
比较例3
PVC K-值58 10% 附注
PVC K-值50 10% 正:符合标准、
四氢呋喃 50% 抗蠕变
环己酮 20% 可填充缝隙
二甲基甲酰胺 5% 负:粘接材料过多时
丁酮 5% 有应力龟裂危险
比较例4
PVC K-值 50 58 63 附注
PVC含量 20 20 20% 正:应力龟裂危险
丁酮 80 70 % 较小
二甲基甲酰胺 10 % 负:不符合标准、
二氯甲烷 80% 不抗蠕变、
缺乏存放稳定性、
热稳定性差
比较例5
PVC K-值 63 10% 附注
PVC K-值 50 10% 正:应力龟裂危险
四氢呋喃 40% 减小,填充缝隙
环己酮 15% 负:不符合标准、
二甲基甲酰胺 5% 缺乏存放稳定性
丁酮 20%
比较例6
PVC K-值 63 10% 附注
PVC K-值 46 10% 正:应力裂缝危险减
四氢呋喃 30% 少、填充缝隙
环己酮 15% 负:不合标准、缺存
丁酮 30% 放稳定性、
二甲基甲酰胺 5% 热稳定性低
实施例7(本发明的粘合剂)
PVC K-值 58 10% 附注
PVC K-值 50 10% 正:符合标准、应力
四氢呋喃 20% 龟裂危险减小、
环己酮 20% 抗蠕变、填充缝
丁酮 35% 隙
二甲基甲酰胺 5% 负:……
实施例8
PVC K-值 58 16% 附注
PVC K-值 50 4% 正:符合标准、应力
四氢呋喃 20% 龟裂减小、
环己酮 20% 抗蠕变、填充
丁酮 35% 缝隙
二甲基甲酰胺 5% 负:…
实施例9(本发明的粘合剂)
PVC K-值 58 10% 附注
PVC K-值 50 10% 正:符合标准,应力
四氢呋喃 35% 龟裂危险减小,
环己酮 15% 抗蠕变,填充缝
丁酮 25% 隙
二甲基甲酰胺 5% 负:…
对产品质量进行技术评价的基础是西德工业标准(DIN)16970。该标准规定内压蠕变试验至少要有1000小时,在室温和60℃下以出现-0.2mm的负隙和+0.6mm正隙考虑。此外还规定最小抗剪强度,-0.2mm时为7N/mm2,+0.6mm时为5N/mm2。
下表为比较例1-6与本发明实施7-9关于内压下的蠕变强度和抗剪强度的比较。
Claims (7)
1、一种硬聚氯乙烯型件的粘合剂,其组成是PVC和混合溶剂为环己酮和/或四氢呋喃、丁酮和二甲基甲酰胺,其特征在于选用K值为58±1和K值为45-52两种分子量的混合PVC,PVC固体含量约为10-30%(重量)(以粘合剂总重量计)。
2、根据权利要求1所述的粘合剂,其特征在于,K值范围较低的溶解PVC组分具有的K值约为49至50。
3、根据权利要求1或2所述的粘合剂,其特征在于它含有不同K-值的PVC类型并以下列比例(以溶解PVC类型的总重量计算百分数)混合:
K值为58±1∶40至85,优先选择范围为45至60;
K值为45-52∶60至15,优先选择范围为55至40。
4、根据权利要求1至3所述的粘合剂,其特征在于该溶剂混合物含有的环状PVC溶剂的量,特别是四氢呋喃和/或环己酮的量约为30-50%,优先选择的是35-45%(以各粘合剂总重量计)。
5、根据权利要求1至4所述的粘合剂,其特征是,该液体溶剂混合物除有限定量的环状溶剂之外还含有非环酮,特别是丁酮;较好的是还混合有小量的二甲基甲酰胺,其中丁酮的量为25-35%(重量)。
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Application Number | Priority Date | Filing Date | Title |
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DEP3512537.3 | 1985-04-06 | ||
DE19853512537 DE3512537A1 (de) | 1985-04-06 | 1985-04-06 | Mittel zum verkleben von formteilen aus hart-pvc |
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CN86102197A CN86102197A (zh) | 1986-10-01 |
CN1004491B true CN1004491B (zh) | 1989-06-14 |
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CA2083676A1 (en) * | 1991-12-17 | 1993-06-18 | Paul E. Naton | Compositions containing hollow microspheres |
US5416142A (en) * | 1991-12-17 | 1995-05-16 | Oatey Company | Method of bonding and bonding compositions |
US5252634A (en) * | 1992-02-18 | 1993-10-12 | Patel Naresh D | Low VOC (volatile organic compounds), solvent-based thermoplastic pipe adhesives which maintain joint adhesive performance |
US5470894A (en) * | 1992-02-18 | 1995-11-28 | Patel; Naresh D. | Low VOC (volatile organic compounds), solvent-based CPVC pipe adhesives which maintain joint adhesive performance |
US5437138A (en) * | 1992-08-13 | 1995-08-01 | Tuohey; Michael E. | Method of making and installing a rain gutter |
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US5562794A (en) * | 1995-03-08 | 1996-10-08 | Basf Corporation | Low solvent, thermoplastic polyurethane containing solvent cement |
US5824724A (en) * | 1995-12-08 | 1998-10-20 | The Lamson & Sessions Co. | Microencapsulatable solvent adhesive composition and method for coupling conduits |
US5821293A (en) * | 1995-12-08 | 1998-10-13 | The Lamson & Sessions Co. | Microencapsulatable solvent adhesive composition and method for coupling conduits |
US6004417A (en) * | 1995-12-08 | 1999-12-21 | The Lamson & Sessions Co. | Method for coupling conduits using microencapsulatable solvent adhesive composition |
US5821289A (en) * | 1996-07-19 | 1998-10-13 | The B.F. Goodrich Company | Low volatile organic solvent based adhesive |
US5817708A (en) * | 1996-07-19 | 1998-10-06 | The B. F. Goodrich Company | Low volatile organic solvent based adhesive |
US5852091A (en) * | 1996-10-04 | 1998-12-22 | Basf Corporation | Solid alcohol-filled PVC pipe cement |
US6087421A (en) * | 1998-09-18 | 2000-07-11 | Ips Corporation | Pentanone-based CPVC adhesives having reduced content of heterocyclic solvents for joining CPVC substrates |
US6887926B1 (en) | 2001-11-16 | 2005-05-03 | Oatey Co. | Bonding compositions for chlorinated polymers and methods of using the same |
DE102004001493A1 (de) * | 2004-01-09 | 2005-08-04 | Henkel Kgaa | Spaltüberbrückender Cyanacrylat-Klebstoff |
US8071675B2 (en) | 2005-12-19 | 2011-12-06 | Loctite (R&D) Limited | Cyanoacrylate composite forming system |
CN101735534B (zh) * | 2010-01-22 | 2011-12-14 | 中国林业科学研究院林产化学工业研究所 | 以马来海松酸盐作为热稳定剂的pvc塑料组合物 |
CN102344770A (zh) * | 2010-08-03 | 2012-02-08 | 福建振云塑业股份有限公司 | 聚氯乙烯管道系统用胶粘剂的配方及制备方法 |
DE102011088123A1 (de) | 2011-12-09 | 2013-06-13 | Henkel Ag & Co. Kgaa | Verfahren zum stoffschlüssigen Verbinden von Kunststoff-Rohren |
DE102012212736A1 (de) | 2012-07-19 | 2014-01-23 | Henkel Ag & Co. Kgaa | Mittel zum Verkleben von Formteilen aus PVC |
JP2017088851A (ja) * | 2015-11-09 | 2017-05-25 | パナソニックIpマネジメント株式会社 | 熱可塑性樹脂用接着剤 |
SE540725C2 (en) * | 2016-06-23 | 2018-10-23 | Ohla Plast & Faergteknik Ab | Use of composition comprising polyvinyl chloride dissolved in1-bytylpyrrolidin-2-one for joining floor panels made of po lyvinyl chloride |
EP3366744B1 (de) | 2017-02-23 | 2021-03-31 | Henkel AG & Co. KGaA | Klebstoffzusammensetzung zum verkleben von formteilen aus kunststoff |
US20220106502A1 (en) * | 2018-12-10 | 2022-04-07 | Advansix Resins & Chemicals Llc | Compositions including pvc or cpvc |
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GB596108A (en) * | 1945-07-19 | 1947-12-29 | Thomas Ernest Atkinson | The cementing of polyvinyl compositions |
DE1032869B (de) * | 1956-12-03 | 1958-06-26 | Mannesmann Ag | Klebemittel aus Polyvinylchlorid mit Tetrahydrofuran als Loesungsmittel und einem Fuellstoff zum Verbinden von Formkoerpern, z. B. Rohren, aus Polyvinylchlorid |
NL278220A (zh) * | 1962-05-08 | 1900-01-01 | ||
FR1359178A (fr) * | 1963-02-12 | 1964-04-24 | Rhovyl Sa | Fibres synthétiques à base de chlorure de polyvinyle |
US3418274A (en) * | 1965-12-15 | 1968-12-24 | Dexter Corp | Liquid coating composition comprising a vinyl chloride dispersion resin, a vinyl chloride copolymer solution resin and acrylic resin in an organic vehicle and metal coated therewith |
DE2126081C3 (de) * | 1971-05-26 | 1979-12-13 | Henkel Kgaa, 4000 Duesseldorf | Verfahren zum Verkleben von Druckrohren aus Polyvinylchlorid |
US4014956A (en) * | 1973-04-23 | 1977-03-29 | Union Carbide Corporation | Thermoplastic powder coating compositions |
US4071479A (en) * | 1976-03-25 | 1978-01-31 | Western Electric Company, Inc. | Reclamation processing of vinyl chloride polymer containing materials and products produced thereby |
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JPS5548239A (en) * | 1978-10-03 | 1980-04-05 | Tokuyama Soda Co Ltd | Polyvinyl chloride composition |
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JPS59230044A (ja) * | 1983-06-13 | 1984-12-24 | Dainichi Seika Kogyo Kk | 塩化ビニル系重合体の分散液 |
JPS6051736A (ja) * | 1983-08-31 | 1985-03-23 | Toyo Soda Mfg Co Ltd | 熱可塑性弾性体組成物 |
JPS60156739A (ja) * | 1984-01-27 | 1985-08-16 | Toyoda Gosei Co Ltd | 軟質樹脂ステアリングホイ−ル |
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1985
- 1985-04-06 DE DE19853512537 patent/DE3512537A1/de not_active Withdrawn
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1986
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- 1986-03-29 DE DE8686104372T patent/DE3680014D1/de not_active Expired - Lifetime
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- 1986-04-02 FI FI861423A patent/FI80289C/fi not_active IP Right Cessation
- 1986-04-02 PT PT82328A patent/PT82328B/pt not_active IP Right Cessation
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- 1986-04-03 CA CA000505721A patent/CA1280240C/en not_active Expired - Fee Related
- 1986-04-04 AU AU55654/86A patent/AU589414B2/en not_active Ceased
- 1986-04-04 BR BR8601559A patent/BR8601559A/pt not_active IP Right Cessation
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- 1986-04-04 ES ES553720A patent/ES8706182A1/es not_active Expired
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- 1986-04-05 CN CN86102197.5A patent/CN1004491B/zh not_active Expired
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1988
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