CN111793352A - 水性聚氨酯粉体粘合剂、弹性材料及其制备方法 - Google Patents
水性聚氨酯粉体粘合剂、弹性材料及其制备方法 Download PDFInfo
- Publication number
- CN111793352A CN111793352A CN202010649270.0A CN202010649270A CN111793352A CN 111793352 A CN111793352 A CN 111793352A CN 202010649270 A CN202010649270 A CN 202010649270A CN 111793352 A CN111793352 A CN 111793352A
- Authority
- CN
- China
- Prior art keywords
- chain extender
- powder adhesive
- polyurethane powder
- raw materials
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 104
- 239000000853 adhesive Substances 0.000 title claims abstract description 90
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 90
- 239000004814 polyurethane Substances 0.000 title claims abstract description 65
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 65
- 239000013013 elastic material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 20
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 150000002902 organometallic compounds Chemical group 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003063 flame retardant Substances 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- -1 carboxylate ion Chemical class 0.000 claims description 20
- 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 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
- 238000009775 high-speed stirring Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 150000007513 acids Chemical group 0.000 claims description 3
- 150000007514 bases Chemical class 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 2
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- STROWIYNZURQQE-UHFFFAOYSA-L disodium 1-phosphonatopropane-1,2-diol Chemical compound [Na+].[Na+].OC(C(C)O)P([O-])([O-])=O STROWIYNZURQQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- DMTRWFMFBIMXBX-UHFFFAOYSA-L lead(2+);6-methylheptanoate Chemical compound [Pb+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O DMTRWFMFBIMXBX-UHFFFAOYSA-L 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
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- 239000010703 silicon Substances 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
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- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 2
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- 238000012360 testing method Methods 0.000 description 12
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- 238000006243 chemical reaction Methods 0.000 description 8
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Abstract
本发明公开了一种水性聚氨酯粉体粘合剂,其包括如下合成原料:二异氰酸酯、多元醇、催化剂、亲水扩链剂、前扩链剂、后扩链剂和溶剂;所述多元醇的平均官能度≥2;所述催化剂为有机金属化合物;所述亲水扩链剂含有亲水性基团或离子,且能与聚合物分子链共价结合;所述前扩链剂和后扩链剂含有两个或以上的活泼氢。所述水性聚氨酯粉体粘合剂为纳米级或微米级的水分散体;经特殊设计的合成原料和合成工艺,使得本粉体粘合剂对粉体和纤维等细小材料的粘结效果比常规的水性聚氨酯粘合剂效果更好,用量更少,粘结强度更高,因此特别适合于粘合粉体、纤维或其它细小材料,干燥固化后具有所需的强度、硬度等性能,可在常温常压条件下粘结粉体而制得弹性材料。
Description
技术领域
本发明属于粉体粘合剂技术领域,尤其涉及一种水性聚氨酯粉体粘合剂及其制备方法,以及含该水性聚氨酯粉体粘合剂的弹性材料及其制备方法。
背景技术
粉体粘合剂是一种用于粘合粉体的粘合剂,其可包围在粉体的表面,在粉体的小颗粒或纤维之间形成连续浸润,使其干燥后形成具有固定形状的材料。
目前已有的粘合剂主要包括以下几类:第一,油性聚氨酯类及发泡聚氨酯类粘结剂;该类粘合剂的VOC含量高,毒性较大,目前正被淘汰。另外,发泡工艺得到的材料强度较低,且存在对施工场地及技术的要求高等缺点。第二,面粘合剂;该类粘合剂一般用于面粘结,通常是将粘合剂涂在被粘物的两个表面之间,将被粘物压合,待粘合剂固化后起到粘结的作用。面粘合剂一般侧重于粘合剂自身的强度、以及粘合剂在被粘面之间的结合强度等方面。而粉体粘合剂的侧重点在于粘合剂对粉体的亲合性和包裹能力、经济性、以及所制材料的整体性能等。某些情况下,面粘合剂中也会添加粉体作为增强剂,这类产品中虽然含有粉体,但其目的是用于面粘结,与粉体粘合剂不同,粉体粘合剂中不含粉体,其作用是将粉体粘结起来,使其成为块体材料,而非用于面粘结。第三,非聚氨酯类水性粘合剂,如丙烯酸树脂、环氧树脂、聚乙烯醇、水泥等。该类粘合剂的弹性较差,粘结粉体后,无法获得弹性材料。第四,通用型水性聚氨酯,这类水性聚氨酯一般用作涂料、面粘结剂等,当使用这类通用型水性聚氨酯作为粉体粘合剂时,由于没有经过针对性的设计,其对粉体的包裹性差,存在粘结性能不足、用量大等问题。
发明内容
为解决上述现有技术中存在的缺点和不足,本发明的第一个目的在于提供一种水性聚氨酯粉体粘合剂及其制备方法,本发明的第二个目的在于提供所述水性聚氨酯粉体粘合剂的用途,以该水性聚氨酯粉体粘合剂粘合粉体或纤维制备弹性材料。
为实现其目的,本发明采取的技术方案如下:
一种水性聚氨酯粉体粘合剂,其包括如下合成原料:二异氰酸酯、多元醇、催化剂、亲水扩链剂、前扩链剂、后扩链剂和溶剂。
本发明合成所述水性聚氨酯粉体粘合剂的主要反应式如下:
m HO-R1-OH+(m+n)OCN-R2-NCO+n HO-R3(-R4)-OH=OCN-(R2-NHCOOR1-OCONH-)mR2-(NHCOOR3(-R4)-OCONHR2-)nNCO,
其中,HO-R1-OH为多元醇,OCN-R2-NCO为二异氰酸酯,n HO-R3(-R4)-OH为亲水扩链剂,R4为亲水基团。
优选地,所述二异氰酸酯的用量为原料中干物质质量的20%~50%。
优选地,所述水性聚氨酯粉体粘合剂的原料中,二异氰酸酯基与羟基的摩尔比为1.0~2.2。本发明中,二异氰酸酯与羟基的摩尔比会影响粘合剂的制备工艺和粘合剂的稳定性,二异氰酸酯与羟基的摩尔比值太大会导致粘合剂的稳定较差,二异氰酸酯与羟基的摩尔比值太小则会导致粘度太大,难以乳化,而以本发明提供的摩尔比进行添加,制备粘合剂时可实现较好的乳化效果,且制备的粘合剂稳定性好。更优选地,二异氰酸酯基与羟基的摩尔比为1.1~1.5,由此,可提供粘结性更好、用量更少的粉体粘合剂。
优选地,所述催化剂的用量为原料中干物质质量的0.02%~1%。
优选地,所述亲水扩链剂的用量为原料中干物质质量的1%~15%。本发明中,亲水扩链剂会对水性乳液的粒径和固含量、以及粘合剂固化后形成的产品的耐水性产生影响。亲水扩链剂的用量越高,则水性乳液的粒径越小,但产品的耐水性越差。亲水扩链剂的用量越低,产品的耐水性越强,但水性乳液的粒径越大。而以上述用量进行添加,水性乳液的粒径为纳米或微米级,且产品的耐水性较好。更优选地,所述亲水扩链剂的用量为原料中干物质质量的3%~7%,可提供粘结性、工艺稳定性最好的粉体粘合剂。
优选地,所述前扩链剂的用量为原料中干物质质量的0~10%。
优选地,所述后扩链剂的用量为原料中干物质质量的0~5%。
所述二异氰酸酯包括TDI(甲苯二异氰酸酯)、MDI(二苯基甲烷二异氰酸酯)、IPDI(异佛尔酮二异氰酸酯)、HMDI(4,4'-二环己基甲烷二异氰酸酯)和HDI(六亚甲基二异氰酸酯)中的至少一种。
所述多元醇的平均官能度≥2。优选地,所述多元醇包括聚醚多元醇类和聚酯多元醇类中的至少一种。优选地,所述二醇包括PPG(丙二醇聚醚)、PTMEG(聚四亚甲基醚二醇)、PEA(聚己二酸乙二醇酯二醇)、PBA(聚己二酸丁二醇酯二醇)、PCL(聚己内酯二醇)中的至少一种。本发明中,多元醇为粘合剂的主体材料,其主要影响胶膜的粘结性、耐水性、强度、硬度和粘合剂的制备工艺等。
所述催化剂为有机金属化合物。优选地,所述催化剂包括有机锡化合物、有机铋化合物、有机铅化合物、有机锌化合物和有机汞化合物中的至少一种。更优选地,所述催化剂包括辛酸亚锡、二月桂酸二丁基锡、异辛酸铋、月桂酸铋、新癸酸铋、环烷酸铋、异辛酸铅、异辛酸锌和异辛酸汞中的至少一种。本发明采用的催化剂可在确保粘合剂性能的前提下,缩短聚合反应的时间,以及降低聚合反应的温度。
所述亲水扩链剂为含有亲水的基团或离子,且能与聚合物分子链共价结合的物质。优选地,所述亲水的基团或离子包括羧基、羧酸根离子、磺酸基、磺酸根离子、磷酸基、磷酸根离子、胺基、铵根离子、以及聚乙二醇链段中的至少一种。优选地,所述亲水扩链剂包括DMPA(二羟甲基丙酸)、DMBA(二羟甲基丁酸)、DHPA(1,2-二羟基-3-丙磺酸钠)、1,4-丁二醇-2-磺酸钠、1,2-二羟基丙膦酸钠、乙二胺基乙磺酸钠、N-甲基二乙醇胺,1-(二亚乙基三胺基)-3-氯-2-丙醇、十二烷基甲基二羟乙基溴化铵、N-甲基-N,N-二(2-羟乙基)甜菜碱、N-甲基-N,N-二(2-羟乙基)-N-(3-磺酸基)丙基铵盐、以及聚乙二醇、聚乙二醇接枝丙二醇中的至少一种。
所述前扩链剂是指含有两个或以上活泼氢的醇类,所述前扩链剂起到调整硬段含量和交联度的作用,从而调整粘合剂固化后的硬度、强度、弹性等力学性能。优选地,所述前扩链剂为小分子的醇类,如:丙二醇、丁二醇、戊二醇、丙三醇、三羟甲基丙烷、季戊四醇等。
所述后扩链剂是指含有两个或以上活泼氢的小分子化合物,所述后扩链剂起到降低异氰酸酯与羟基比值的作用,从而增加粘合剂的分子量,提高粘合剂固化后的硬度、强度、弹性等力学性能。优选地,所述后扩链剂为小分子的醇类、胺类或醇胺类,如:丙二醇、丁二醇、戊二醇、丙三醇、乙二胺、对苯二胺、二乙烯三胺、三乙烯四胺、二乙醇胺、或三乙醇胺等。
所述溶剂是指能溶解各种反应物,或能促进反应物之间互相溶解,或可以降低反应体系粘度的有机溶剂。优选地,所述溶剂的用量为原料中干物质质量的0~400%。溶剂添加量可变化范围较大,主要是由于受不同的二异氰酸酯与羟基摩尔比、不同的前扩链剂的官能度和加入量的影响,预聚体粘度可在极大范围内改变,当粘度较大时,需加入大量的溶剂来降低预聚体的粘度,以便正常乳化;而粘度较小时,可少加甚至不加溶剂,以节约成本。因此,本发明中,溶剂的添加量由预聚体的粘度决定,而预聚体的粘度为100~500mPa·s时利于乳化。优选地,所述溶剂为DMF(二甲基甲酰胺)、NMP(N-甲基吡咯烷酮)、丙酮或丁酮等。
所述亲水扩链剂为酸性或碱性化合物时,所述水性聚氨酯粉体粘合剂的合成原料还包括成盐剂;所述成盐剂能与所述亲水扩链剂发生中和反应,生成离子化合物。
优选地,所述成盐剂与所述亲水扩链剂的当量比为0.8~1.2。
所述亲水扩链剂为酸性化合物时,所述成盐剂为碱性化合物,如:氨水、三乙胺、二乙烯三胺和三乙醇胺中的至少一种。
所述亲水扩链剂为碱性化合物时,所述成盐剂为酸性化合物或卤化物,如:甲酸、乙酸、丙酸、氯丁烷和环氧氯丙烷中的至少一种。
优选地,所述水性聚氨酯粉体粘合剂的合成原料还包括结合力促进剂,所述结合力促进剂是指能进一步提升水性聚氨酯与粉体或纤维的界面结合力的物质。优选地,所述结合力促进剂的用量为原料总质量的0.01%~1%。优选地,所述结合力促进剂包括硅烷偶联剂、钛酸酯类偶联剂、铝酸酯类偶联剂、表面活性剂中的至少一种。更优选地,所述结合力促进剂包括三甲氧基硅烷偶联剂、三乙氧基硅烷偶联剂、钛酸四丁酯、二硬脂酰氧异丙基铝酸酯、硬脂酸、聚丙烯酸钠中的至少一种。
优选地,所述水性聚氨酯粉体粘合剂的合成原料还包括阻燃剂,所述阻燃剂的用量为原料总质量的0~40%。优选地,所述阻燃剂包括锑系阻燃剂、镁系阻燃剂、铝系阻燃剂、硅系阻燃剂、卤系阻燃剂、磷系阻燃剂、氮系阻燃剂中的至少一种。更优选地,所述阻燃剂包括三氧化二锑、氢氧化镁、氢氧化铝、硅酮聚合物、氯化石蜡、十溴二苯醚、聚磷酸铵、三聚氰胺、N,N-二羟乙基胺甲基磷酸二乙酯中的至少一种。
所述水性聚氨酯粉体粘合剂的制备方法为:将二异氰酸酯、多元醇、催化剂、亲水扩链剂、前扩链剂和溶剂混合,在搅拌下60~100℃反应0.5~6h,得到预聚物,然后将上述预聚物与水在高速搅拌下混合乳化,加入后扩链剂,混合均匀,脱去溶剂,制得所述水性聚氨酯粉体粘合剂。
所述脱去溶剂为采用现有常规使用的方法进行,如:加热和/或抽真空。
优选地,所述预聚物与水的质量比为1:(0.6~5)。该配比下,乳化效果较好。
所述水性聚氨酯粉体粘合剂的合成原料含有所述成盐剂时,将所述预聚物与所述成盐剂进行混合搅拌,中和。
所述结合力促进剂和所述阻燃剂视其物质种类,可先加入预聚物中,也可后添加到粘合剂中,或者在制备弹性材料时添加到粉体或纤维中。
所述水性聚氨酯粉体粘合剂为纳米级或微米级的水分散体,适用于粘合粉体、纤维或其它细小材料。
本发明还提供了一种弹性材料,其包括如下组分:所述水性聚氨酯粉体粘合剂、粉体或纤维、以及助剂。
优选地,所述水性聚氨酯粉体粘合剂与粉体或纤维的干物质质量比为(0.1~2):1。
优选地,所述粉体包括但不限于陶土、滑石粉、云母粉、长石粉、膨润土、石棉粉、煤矸石粉、粉煤灰、海泡石粉、海泡石粉、碳酸钙、蒙脱土、玻璃微珠、水泥、砂子和石墨粉中的至少一种。
优选地,所述纤维包括玻璃纤维、碳纤维、芳纶纤维、奥纶纤维、聚酯纤维、尼龙纤维、维尼纶纤维、聚丙烯纤维、聚酰亚胺纤维、棉纤维、剑麻、纸纤维等。
所述粉体或纤维可以是经过改性处理的或者是未经过改性处理的。
优选地,所述助剂为防霉剂、流平剂、阻燃剂或消泡剂等,以制备具有相应功能的弹性材料。优选地,所述助剂的添加量为弹性材料原料总质量的5%以下。
所述弹性材料的制备方法为:将所有组份混合均匀,得到浆料;使所述浆料成型,干燥,得到所述弹性材料。
本发明中,将所述浆料干燥后,即可制备出不同形状的弹性材料。所述浆料也可倒入不同形状的模具中再进行干燥。弹性材料还可进一步加工,如雕刻等,且在加工过程中,如出现操作失误等而造成材料缺失,可通过填充浆料来补救。新补加的浆料固化后即与原材料形成一体结构,无缝连接。而现有技术采用挤出机制备的发泡型材,若在加工过程中操作失误,将直接导致产品报废,难以补救。
本发明所述弹性材料的制备在常温常压条件下进行,制备过程简单,操作方便,制备成本低。
与现有技术相比,本发明的有益效果为:本发明通过调整异氰酸酯与羟基的比值、亲水扩链剂的种类与含量、成盐剂的种类与含量、交联多元醇的种类与含量、催化剂的种类与含量、前扩链剂和后扩链剂的种类与含量、阻燃剂的种类与含量、溶剂的种类与用量、预聚反应的温度和时间等,合成了对粉体和纤维具有良好的亲和性和包裹能力的水性聚氨酯粉体粘合剂,该水性聚氨酯粉体粘合剂为环保型水性粘合剂,使用方便,对粉体和纤维等细小材料的粘结效果好,可在常温常压下通过简单的模具制得具有固定形状的和所需强度、硬度等性能的弹性材料,且粘合剂的用量少,制备成本低。
具体实施方式
为更好的说明本发明的目的、技术方案和优点,本发明通过下列实施例进一步说明。显然,下列实施例仅是本发明的一部分实施例,而不是全部的实施例。应理解,本发明实施例仅用于说明本发明的技术效果,而非用于限制本发明的保护范围。
实施例1
将下列质量份的原料加入到反应釜中:
搅拌下70℃反应2h,加入6份三乙胺(成盐剂)中和,然后在1000RPM以上的高速搅拌下倒入200份水中乳化,加入1份二乙烯三胺(后扩链剂),搅拌均匀,真空加热脱去溶剂,制得水性聚氨酯粉体粘合剂。
取上述水性聚氨酯粉体粘合剂100份、50份碳酸钙、30份氢氧化镁、10份硫酸钡、8份长石粉、2份钛酸四丁酯、10份乙二醇二甲醚、1份聚乙二醇接枝聚二甲基硅氧烷和0.1份甲基异噻唑啉酮,混合搅拌均匀,得到浆料。将浆料倒入模具中,自然晾干,得到厚度为2mm的板材。
对板材进行性能测试,结果如下表所示:
测试项目 | 实施例1的板材 |
强度/MPa | 23.1 |
断裂伸长率/% | 405 |
损耗因子@25℃ | 0.42 |
5J冲击峰值力/N | 2327 |
从上述测试结果可看出,该板材的损耗因子较大,具有较好的减震和缓冲的效果,适合用作缓冲材料。
实施例2
将下列质量份的原料加入到反应釜中:
搅拌下60℃反应2h,加入7份三乙醇胺(成盐剂)中和,然后在1000RPM以上的高速搅拌下倒入200份水中乳化,加入1份二乙烯三胺(后扩链剂),搅拌均匀,真空加热脱去溶剂,制得水性聚氨酯粉体粘合剂。
取上述水性聚氨酯粉体粘合剂100份、55份碳酸钙、25份氢氧化镁、10份硫酸钡、8份长石粉、2份钛酸四丁酯、10份乙二醇甲醚乙酸酯、0.2份聚乙二醇接枝聚二甲基硅氧烷和0.1份甲基异噻唑啉酮,混合搅拌均匀,得到浆料。将浆料倒入模具中,自然晾干,得到厚度为2mm的板材。
对板材进行性能测试,结果如下表所示:
从上述测试结果可看出,本实施例的水性聚氨酯粉体粘合剂中采用了分子链段柔性极好的PTMG作为多元醇,因此其弹性较好,相应制得的板材的强度和弹性也较好,损耗因子适中,具有缓冲和反弹冲力的作用,可用作弹性及缓冲材料。
实施例3
将下列质量份的原料加入到反应釜中:
搅拌下60℃反应2h,加入3份三乙醇胺(成盐剂)中和,然后在1000RPM以上的高速搅拌下倒入200份水中乳化,加入1份乙二胺(后扩链剂),搅拌均匀,真空加热脱去溶剂,制得水性聚氨酯粉体粘合剂。
取上述水性聚氨酯粉体粘合剂100份、40份碳酸钙、25份氢氧化镁、15份玻纤粉、10份硫酸钡、8份长石粉、2份钛酸四丁酯、10份乙二醇甲醚乙酸酯、0.2份聚乙二醇接枝聚二甲基硅氧烷和0.1份甲基异噻唑啉酮,混合搅拌均匀,得到浆料。将浆料倒入模具中,自然晾干,得到厚度为2mm的板材。
对板材进行性能测试,结果如下表所示:
从上述测试结果可看出,本实施例的水性聚氨酯粉体粘合剂不仅采用了柔性极好的PTMG和HDI作为主体原料,还使用三官能度的前扩链剂对聚氨酯分子进行了交联,使得板材的弹性极佳,常温下损耗因子较低,适合用作弹性材料,如弹性墙、弹性地面等。
实施例4
将下列质量份的原料加入到反应釜中:
搅拌下60℃反应2h,加入9份三乙醇胺(成盐剂)中和,然后在1000RPM以上的高速搅拌下倒入200份水中乳化,加入1份二乙烯三胺(后扩链剂),搅拌均匀,真空加热脱去溶剂,制得水性聚氨酯粉体粘合剂。
取上述水性聚氨酯粉体粘合剂100份、98份碳酸钙、2份钛酸四丁酯、0.2份聚乙二醇接枝聚二甲基硅氧烷和0.1份甲基异噻唑啉酮,混合搅拌均匀,得到浆料。将浆料倒入模具中,自然晾干,得到厚度为2mm的板材。
对板材进行性能测试,结果如下表所示:
测试项目 | 实施例4的板材 |
强度/MPa | 32.2 |
断裂伸长率/% | 210 |
100%弹性模量/MPa | 16.05 |
邵氏硬度 | 92A |
从上述测试结果可看出,本实施例的水性聚氨酯粉体粘合剂采用了较高的异氰酸酯基与羟基的比例,以及较高的前扩链剂含量以确保硬段含量较高,还加入了较多的三官能度前扩链剂对聚氨酯分子进行交联,使得粘结粉体后固化得到的板材的强度和硬度较高,可用于室内雕塑修补、缝隙填充等用途。
实施例5
将下列质量份的原料加入到反应釜中:
搅拌下在80℃反应2h,加入6份三乙胺(成盐剂)中和,然后在1000RPM以上的高速搅拌下倒入200份水中乳化,加入1份二乙烯三胺(后扩链剂),搅拌均匀,真空加热脱去溶剂,制得水性聚氨酯粉体粘合剂。
取上述水性聚氨酯粉体粘合剂100份、50份碳酸钙、30份氢氧化镁、10份硫酸钡、8份长石粉、2份钛酸四丁酯、10份乙二醇二甲醚、1份聚乙二醇接枝聚二甲基硅氧烷和0.1份甲基异噻唑啉酮,混合搅拌均匀,得到浆料。将浆料倒入模具中,自然晾干,得到厚度为2mm的板材。
板材的性能测试:
测试项目 | 实施例5的板材 |
强度/MPa | 39.4 |
断裂伸长率/% | 344 |
100%弹性模量/MPa | 12.02 |
从上述测试结果可看出,本实施例的板材的力学性能较好,适合于一些同时对力学性能要求较高的应用。
对比例1
将市售通用型水性聚氨酯(本对比例采用“朗*”牌769型水性聚氨酯)100份、50份碳酸钙、30份氢氧化镁、10份硫酸钡、8份长石粉、2份钛酸四丁酯、10份乙二醇二甲醚、1份聚乙二醇接枝聚二甲基硅氧烷、0.1份甲基异噻唑啉酮和100份水,混合搅拌均匀,得到浆料。将浆料倒入模具中,自然晾干,得到厚度为2mm的板材。
对板材进行性能测试,结果如下表所示:
测试项目 | 对比例1的板材 |
强度/MPa | 11.2 |
断裂伸长率/% | 237 |
损耗因子@25℃ | 0.31 |
5J冲击峰值力/N | 2927 |
从上述测试结果可看出,对比例1的板材的强度和断裂伸长率均明显低于实施例1的板材,说明其粉体间的粘结效果较差,从而造成板材的力学性能较差。另外,对比例1的板材的损耗因子明显低于实施例1的板材,5J冲击峰值力明显高于实施例1的板材,说明对比例1的板材缓冲性能较差。
由此证明,通用型水性聚氨酯粘合剂用于粉体粘结时,存在粘结性差的问题,获得的板材的力学性能和缓冲性能也较差,无法满足实际需求。
对比例2
将市售“昕*”牌DS155型水性丙烯酸树脂100份、50份碳酸钙、30份氢氧化镁、10份硫酸钡、8份长石粉、2份钛酸四丁酯、10份乙二醇二甲醚、1份聚乙二醇接枝聚二甲基硅氧烷、0.1份甲基异噻唑啉酮和100份水,混合搅拌均匀,得到浆料。将浆料倒入模具中,自然晾干,得到厚度为2mm的板材。
对板材进行性能测试,结果如下表所示:
从上述测试结果可看出,水性丙烯酸树脂用于粉体粘结时,存在弹性和缓冲性能较差的问题,无法满足实际要求。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种水性聚氨酯粉体粘合剂,其特征在于,包括如下合成原料:二异氰酸酯、多元醇、催化剂、亲水扩链剂、前扩链剂、后扩链剂和溶剂;所述多元醇的平均官能度≥2;所述催化剂为有机金属化合物;所述亲水扩链剂含有亲水的基团或离子,且能与聚合物分子链共价结合;所述前扩链剂和后扩链剂均含有两个或以上的活泼氢。
2.如权利要求1所述的水性聚氨酯粉体粘合剂,其特征在于,所述水性聚氨酯粉体粘合剂的合成原料中,所述二异氰酸酯的用量为原料中干物质质量的20%~50%,所述二异氰酸酯基与羟基的摩尔比为1.0~2.2,所述亲水扩链剂的用量为原料中干物质质量的1%~15%,所述催化剂的用量为原料中干物质质量的0.02%~1%;
优选地,所述二异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯和六亚甲基二异氰酸酯中的至少一种;
优选地,所述多元醇包括聚醚多元醇类、聚酯多元醇类中的至少一种;
优选地,所述催化剂为有机金属化合物;所述有机金属化合物包括有机锡化合物、有机铋化合物、有机铅化合物、有机锌化合物和有机汞化合物中的至少一种;更优选地,所述催化剂包括辛酸亚锡、二月桂酸二丁基锡、异辛酸铋、月桂酸铋、新癸酸铋、环烷酸铋、异辛酸铅、异辛酸锌和异辛酸汞中的至少一种;
优选地,所述亲水扩链剂含有羧基、羧酸根离子、磺酸基、磺酸根离子、磷酸基、磷酸根离子、胺基、铵根离子、以及聚乙二醇链段中的至少一种;更优选地,所述亲水扩链剂包括二羟甲基丙酸、二羟甲基丁酸、1,2-二羟基-3-丙磺酸钠、1,4-丁二醇-2-磺酸钠、1,2-二羟基丙膦酸钠、乙二胺基乙磺酸钠、N-甲基二乙醇胺,1-(二亚乙基三胺基)-3-氯-2-丙醇、十二烷基甲基二羟乙基溴化铵、N-甲基-N,N-二(2-羟乙基)甜菜碱、N-甲基-N,N-二(2-羟乙基)-N-(3-磺酸基)丙基铵盐、聚乙二醇、聚乙二醇接枝丙二醇中的至少一种。
3.如权利要求1所述的水性聚氨酯粉体粘合剂,其特征在于,所述亲水扩链剂为酸性或碱性化合物时,所述水性聚氨酯粉体粘合剂的合成原料还包括成盐剂;所述成盐剂能与所述亲水扩链剂发生中和反应;
优选地,所述成盐剂与所述亲水扩链剂的当量比为0.8~1.2。
4.如权利要求1所述的水性聚氨酯粉体粘合剂,其特征在于,所述水性聚氨酯粉体粘合剂的合成原料还包括结合力促进剂;
优选地,所述结合力促进剂的用量为原料总质量的0.01%~1%;
优选地,所述结合力促进剂包括硅烷偶联剂、钛酸酯类偶联剂、铝酸酯类偶联剂、表面活性剂中的至少一种;
更优选地,所述结合力促进剂包括三甲氧基硅烷偶联剂、三乙氧基硅烷偶联剂、钛酸四丁酯、二硬脂酰氧异丙基铝酸酯、硬脂酸、聚丙烯酸钠中的至少一种。
5.如权利要求1所述的水性聚氨酯粉体粘合剂,其特征在于,所述水性聚氨酯粉体粘合剂的合成原料还包括阻燃剂;优选地,所述阻燃剂的用量为原料总质量的0~40%;
优选地,所述阻燃剂包括锑系阻燃剂、镁系阻燃剂、铝系阻燃剂、硅系阻燃剂、卤系阻燃剂、磷系阻燃剂、氮系阻燃剂中的至少一种;
更优选地,所述阻燃剂包括三氧化二锑、氢氧化镁、氢氧化铝、硅酮聚合物、氯化石蜡、十溴二苯醚、聚磷酸铵、三聚氰胺、N,N-二羟乙基胺甲基磷酸二乙酯中的至少一种。
6.如权利要求1~5任一项所述的水性聚氨酯粉体粘合剂的制备方法,其特征在于,包括如下步骤:将二异氰酸酯、多元醇、催化剂、亲水扩链剂、前扩链剂和溶剂混合,在搅拌下60~100℃反应0.5~6h,得到预聚物,然后将上述预聚物与水在高速搅拌下混合乳化,加入后扩链剂,混合均匀,脱去有机溶剂,制得所述水性聚氨酯粉体粘合剂。
7.如权利要求6所述的水性聚氨酯粉体粘合剂的制备方法,其特征在于,所述预聚物与水的质量比为1:(0.6~5)。
8.如权利要求6所述的水性聚氨酯粉体粘合剂的制备方法,其特征在于,所述水性聚氨酯粉体粘合剂的合成原料含有所述成盐剂时,将所述预聚物与所述成盐剂进行混合搅拌,中和。
9.一种弹性材料,其特征在于,包括如下组份:如权利要求1~5任一项所述的水性聚氨酯粉体粘合剂、粉体或纤维、以及助剂。
10.如权利要求9所述的弹性材料的制备方法,其特征在于,包括如下步骤:将所有组份混合均匀,得到浆料;使所述浆料成型,干燥,得到所述弹性材料。
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Address after: 516200, No. 12 Zhongchang Power Plant Road, Xiayong Petrochemical Avenue, Daya Bay, Huizhou, Guangdong Province Patentee after: HUIZHOU DAYAWAN DAZHI FINE CHEMICAL Co.,Ltd. Country or region after: China Address before: No. 5, Keji Road, Science and Technology Innovation Park, West District, Daya Bay, Huizhou City, Guangdong Province, 516000 Patentee before: HUIZHOU DAYAWAN DAZHI FINE CHEMICAL Co.,Ltd. Country or region before: China |