一种具有高强度、低翘曲和高热变形温度的玻纤增强PBT/PC合金及其制备方法和应用A glass fiber reinforced PBT/PC alloy with high strength, low warpage and high heat distortion temperature and its preparation method and application
技术领域technical field
本发明涉及高分子材料技术领域,更具体地涉及一种具有高强度、低翘曲和高热变形温度的玻纤增强PBT/PC合金及其制备方法和应用。The invention relates to the technical field of polymer materials, and more particularly to a glass fiber reinforced PBT/PC alloy with high strength, low warpage and high thermal deformation temperature, and a preparation method and application thereof.
背景技术Background technique
PBT树脂是一种结晶性的热塑性塑料,结晶速度快,具有耐化学药品性、耐热性好等优点,但是又存在成型收缩率大、缺口冲击强度低等缺点。PC作为一种非结晶型工程塑料,综合性能优异,特别是冲击强度高、尺寸稳定性好,但PC流动性差、耐溶剂性差、易磨损且价格较高。将PBT与PC共混,可取长补短,得到综合性能优异的合金材料。在家电和风扇行业中,为了解决玻纤增强PBT翘曲的问题,常在PBT中加入PC。但是,PBT和PC共混,由于钛酸酯类催化剂的残留,在挤出过程中会发生酯交换反应,使得合金的结晶温度降低,成型时间延长,热变形温度降低,耐热性下降。目前主要通过加入酯交换抑制剂来抑制两者的酯交换反应。PBT resin is a crystalline thermoplastic with fast crystallization speed, chemical resistance and good heat resistance, but it also has disadvantages such as large molding shrinkage and low notched impact strength. As an amorphous engineering plastic, PC has excellent comprehensive properties, especially high impact strength and good dimensional stability, but PC has poor fluidity, poor solvent resistance, easy wear and high price. Blending PBT and PC can complement each other's strengths to obtain alloy materials with excellent comprehensive properties. In the home appliance and fan industry, in order to solve the problem of warpage of glass fiber reinforced PBT, PC is often added to PBT. However, when PBT and PC are blended, due to the residual titanate catalyst, the transesterification reaction will occur during the extrusion process, which reduces the crystallization temperature of the alloy, prolongs the molding time, reduces the heat distortion temperature, and reduces the heat resistance. At present, the transesterification reaction of the two is mainly inhibited by adding transesterification inhibitors.
现有技术中,如CN106336640A公开采用聚碳化二亚胺、无水磷酸二氢钠(AMSP)、磷酸三苯酯(TPP)等作为酯交换抑制剂来猝灭PBT中残余的催化剂从而抑制酯交换反应,使PC/PBT耐热性能更好。但是,仅采用酯抑制剂的手段对性能的改善依然有限,有必要作进一步的改善。In the prior art, as disclosed in CN106336640A, polycarbodiimide, anhydrous sodium dihydrogen phosphate (AMSP), triphenyl phosphate (TPP), etc. are used as transesterification inhibitors to quench residual catalysts in PBT to inhibit transesterification. The reaction makes PC/PBT better heat resistance. However, the improvement of performance is still limited only by means of ester inhibitors, and further improvement is necessary.
发明内容SUMMARY OF THE INVENTION
本发明的目的是为了克服现有技术的不足,提供一种具有高强度、低翘曲和高热变形温度的玻纤增强PBT/PC合金。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a glass fiber reinforced PBT/PC alloy with high strength, low warpage and high heat distortion temperature.
本发明的另一个目的在于提供所述PBT/PC合金的制备方法。Another object of the present invention is to provide a preparation method of the PBT/PC alloy.
本发明的另一个目的在于提供所述PBT/PC合金的应用。Another object of the present invention is to provide applications of the PBT/PC alloy.
本发明上述目的通过如下技术方案予以实现:The above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种高强度、高热变形温度的玻纤增强PBT/PC合金,按重量份计算,包括如下组分:A glass fiber reinforced PBT/PC alloy with high strength and high heat distortion temperature, calculated in parts by weight, comprising the following components:
PBT树脂 37.3~64.6%;PBT resin 37.3~64.6%;
PC树脂 10~37.3%;PC resin 10~37.3%;
玻璃纤维 25~40%;Glass fiber 25~40%;
酯交换抑制剂 0.2~1.5%;Transesterification inhibitor 0.2~1.5%;
抗氧剂 0.2~0.5%;Antioxidant 0.2~0.5%;
所述PBT树脂为端羧基含量不高于10mmol/kg的PBT树脂,端羧基含量测试方法根据GB/T 14190-2017;Described PBT resin is the PBT resin that terminal carboxyl group content is not higher than 10mmol/kg, and the test method of terminal carboxyl group content is according to GB/T 14190-2017;
所述PC树脂是端羟基含量不高于10ppm的PC树脂;Described PC resin is PC resin with terminal hydroxyl content not higher than 10ppm;
所述酯交换抑制剂为聚碳化二亚胺。The transesterification inhibitor is polycarbodiimide.
端羟基含量的测试方法如下:用Bruker AVANCE Ⅲ HD 600MHz核磁仪测试PC树脂的31P核磁共振波谱。以浓度为4.0mg/mL的环己醇作为内标物,以浓度为5mg/mL的乙酰丙酮铬作为松弛剂,以2-氯-4,4,5,5-四甲基-1,3,2-二噁磷杂戊环作为磷化试剂。将25mgPC树脂溶解于400μL氘代吡啶/氘代氯仿(体积比1.6:1)中,加入150μL松弛剂,150μL内标物和75μL磷化试剂作为测试样品。测试条件:室温,90°脉冲角度,25s脉冲间隔,250s信号采集时间,61.9ppm扫描宽度。端羟基含量计算如下:The test method of terminal hydroxyl group content is as follows: use Bruker AVANCE III HD 600MHz nuclear magnetic resonance instrument to test the 31P nuclear magnetic resonance spectrum of PC resin. Cyclohexanol at a concentration of 4.0 mg/mL was used as the internal standard, chromium acetylacetonate at a concentration of 5 mg/mL was used as a relaxant, and 2-chloro-4,4,5,5-tetramethyl-1,3 , 2-dioxaphospholane as a phosphating reagent. 25 mg PC resin was dissolved in 400 μL deuterated pyridine/deuterated chloroform (volume ratio 1.6:1), 150 μL relaxation agent, 150 μL internal standard and 75 μL phosphating reagent were added as test samples. Test conditions: room temperature, 90° pulse angle, 25s pulse interval, 250s signal acquisition time, 61.9ppm scan width. The hydroxyl terminal content is calculated as follows:
其中A(ppm)是PC树脂的端羟基含量;c是内标物的浓度;150(μL)是内标物的体积;100.16(mmg/mmol)是环己醇的摩尔质量;m(mg)是PC树脂的质量;B
1是PC树脂的端羟基峰面积,B
2是环己醇的羟基峰面积。
where A (ppm) is the content of terminal hydroxyl groups of PC resin; c is the concentration of the internal standard; 150 (μL) is the volume of the internal standard; 100.16 (mmg/mmol) is the molar mass of cyclohexanol; m (mg) is the mass of the PC resin; B 1 is the terminal hydroxyl peak area of the PC resin, and B 2 is the hydroxyl peak area of cyclohexanol.
发明人意外发现,控制PBT树脂的端羧基含量及PC树脂的端羟基含量在上述范围内,能使PBT/PC合金的拉伸强度、热变形温度、翘曲度得到进一步的提高。PBT/PC合金在生产过程中会发生酯交换反应,使得材料的力学性能和热变形温度下降,PBT的端羧基和PC的端羟基会加剧酯交换反应,而通过选取低端羧基含量的PBT和低端羟基含量的PC,同时加入酯交换抑制剂聚碳化二亚胺,可以抑制酯交换反应,从而提高材料的性能。The inventor unexpectedly found that controlling the content of terminal carboxyl groups of PBT resin and the content of terminal hydroxyl groups of PC resin within the above ranges can further improve the tensile strength, heat distortion temperature and warpage of PBT/PC alloys. In the production process of PBT/PC alloy, the transesterification reaction will occur, which will reduce the mechanical properties and thermal deformation temperature of the material, and the terminal carboxyl group of PBT and the terminal hydroxyl group of PC will aggravate the transesterification reaction. PC with low-end hydroxyl content and polycarbodiimide, a transesterification inhibitor, can inhibit the transesterification reaction, thereby improving the performance of the material.
更优选地,所述PBT树脂为端羧基含量为1~10mmol/Kg的PBT树脂。More preferably, the PBT resin is a PBT resin with a terminal carboxyl group content of 1-10 mmol/Kg.
更优选地,所述PC树脂是端羟基含量为1~10ppm的PC树脂。More preferably, the PC resin is a PC resin with a terminal hydroxyl group content of 1-10 ppm.
本发明所述的PBT、PC均可在市面购买。The PBT and PC of the present invention can be purchased in the market.
优选地,所述玻璃纤维为平均直径为7~17μm,平均长度为3~5mm的玻璃 纤维。Preferably, the glass fibers are glass fibers with an average diameter of 7-17 μm and an average length of 3-5 mm.
本发明所述玻璃纤维种类不限,优选为无碱玻璃纤维。The types of glass fibers described in the present invention are not limited, and are preferably alkali-free glass fibers.
本发明所述抗氧剂可选自常用的抗氧剂。优选地,所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫代酯类抗氧剂中的一种或几种。The antioxidant of the present invention can be selected from commonly used antioxidants. Preferably, the antioxidant is one or more of hindered phenol antioxidants, phosphite antioxidants, and thioester antioxidants.
所述PBT/PC合金的制备方法,包括如下步骤:The preparation method of the PBT/PC alloy comprises the following steps:
S1.PBT树脂、PC树脂进行烘干;S1. PBT resin and PC resin are dried;
S2.将S1.烘干后的PBT树脂、PC树脂与聚碳化二亚胺,抗氧剂混合,从双螺杆挤出机的主喂料口喂料,玻璃纤维从双螺杆挤出机的侧喂料口喂料;S2. Mix the dried PBT resin and PC resin of S1. with polycarbodiimide and antioxidant, and feed the materials from the main feeding port of the twin-screw extruder. The glass fiber is fed from the side of the twin-screw extruder. feeding port feeding;
S3.设置双螺杆挤出机各区的温度为220~250℃,进行挤出;S3. Set the temperature of each zone of the twin-screw extruder to 220-250°C, and extrude;
S4.挤出后进行后处理,得到所述PBT/PC合金。S4. Perform post-processing after extrusion to obtain the PBT/PC alloy.
优选地,S1.中,烘干的条件为在120~140℃下烘干4~6h。Preferably, in S1., the drying conditions are drying at 120-140° C. for 4-6 hours.
优选地,S3.中,双螺杆挤出机的转速为300-400rpm。Preferably, in S3., the rotational speed of the twin-screw extruder is 300-400 rpm.
优选地,S4.中,所述后处理包括冷却、风干、切粒、包装等步骤。Preferably, in S4., the post-processing includes cooling, air drying, dicing, packaging and other steps.
所述PBT/PC合金在制备兼具高强度、高热变形温度、低翘曲性能的产品中的应用。更具体地,所述产品为家电产品。The application of the PBT/PC alloy in the preparation of products with high strength, high heat distortion temperature and low warpage properties. More specifically, the product is a home appliance product.
与现有技术相比,本发明具有如下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
本发明所述PBT/PC合金,通过对PBT中端羧基含量及PC中端羟基含量的选择,使得合金具有更佳的拉伸强度、热变形温度、翘曲度,所述合金的拉伸强度>130MPa,热变形温度>120℃,翘曲度<3mm,可以应用于要求高热变形温度,低翘曲的家电产品上。The PBT/PC alloy of the present invention has better tensile strength, heat distortion temperature, and warpage through the selection of the content of terminal carboxyl groups in PBT and the content of terminal hydroxyl groups in PC, and the tensile strength of the alloy is improved. >130MPa, heat distortion temperature >120℃, warpage <3mm, it can be applied to household appliances requiring high heat distortion temperature and low warpage.
具体实施方式Detailed ways
下面结合具体实施例和对比例对本发明做进一步的详细说明,但本发明并不限于下述实施例。The present invention will be further described in detail below in conjunction with specific examples and comparative examples, but the present invention is not limited to the following examples.
实施例中,未有特别说明的原料均为常规市售商品。In the examples, the raw materials without special instructions are all conventional commercial products.
PBT树脂1:选用仪征GX121J,端羧基含量为8mmol/kg;PBT resin 1: Yizheng GX121J is selected, and the content of terminal carboxyl groups is 8mmol/kg;
PBT树脂2:选用仪征GX122J,端羧基含量为4mmol/kg;PBT resin 2: Yizheng GX122J is selected, and the content of terminal carboxyl groups is 4mmol/kg;
PBT树脂3:选用仪征GX110,端羧基含量为24mmol/kg;PBT resin 3: choose Yizheng GX110, the content of terminal carboxyl group is 24mmol/kg;
PC树脂1:选用韩国三养3030PJ,端羟基含量为3ppm;PC resin 1: South Korea's Samyang 3030PJ is selected, and the content of terminal hydroxyl groups is 3ppm;
PC树脂2:选用LG、1300 03 NP,端羟基含量为8ppm;PC resin 2: LG, 1300 03 NP are selected, and the content of terminal hydroxyl groups is 8ppm;
PC树脂3:选用日本出光FN2200,端羟基含量为150ppm;PC resin 3: Idemitsu FN2200 is selected from Japan, and the content of terminal hydroxyl groups is 150ppm;
玻璃纤维,选用ECS13-3.0-T436W(无碱玻纤,玻纤平均直径13μm,平均长度3.0mm,泰山玻璃纤维有限公司)Glass fiber, choose ECS13-3.0-T436W (alkali-free glass fiber, glass fiber average diameter 13μm, average length 3.0mm, Taishan Glass Fiber Co., Ltd.)
酯交换抑制剂:选用Stabilizer 9000聚碳化二亚胺(昆山鼎发化工);Transesterification inhibitor: use Stabilizer 9000 polycarbodiimide (Kunshan Dingfa Chemical);
抗氧剂:分别选用RIANOX 1010,RIANOX 168(利安隆)。Antioxidant: RIANOX 1010 and RIANOX 168 (Rianlong) were selected respectively.
测试方法:testing method:
PBT树脂中,端羧基含量测试方法根据GB/T 14190-2017;In PBT resin, the test method of terminal carboxyl group content is according to GB/T 14190-2017;
PC树脂中,端羟基含量的测试方法如下:用Bruker AVANCE Ⅲ HD 600MHz核磁仪测试PC树脂的31P核磁共振波谱。以浓度为4.0mg/mL的环己醇作为内标物,以浓度为5mg/mL的乙酰丙酮铬作为松弛剂,以2-氯-4,4,5,5-四甲基-1,3,2-二噁磷杂戊环作为磷化试剂。将25mgPC树脂溶解于400μL氘代吡啶/氘代氯仿(体积比1.6:1)中,加入150μL松弛剂,150μL内标物和75μL磷化试剂作为测试样品。测试条件:室温,90°脉冲角度,25s脉冲间隔,250s信号采集时间,61.9ppm扫描宽度。端羟基含量计算如下:In the PC resin, the test method for the content of terminal hydroxyl groups is as follows: The 31P nuclear magnetic resonance spectrum of the PC resin is tested with a Bruker AVANCE III HD 600MHz nuclear magnetic resonance instrument. Cyclohexanol at a concentration of 4.0 mg/mL was used as the internal standard, chromium acetylacetonate at a concentration of 5 mg/mL was used as a relaxant, and 2-chloro-4,4,5,5-tetramethyl-1,3 , 2-dioxaphospholane as a phosphating reagent. 25 mg PC resin was dissolved in 400 μL deuterated pyridine/deuterated chloroform (volume ratio 1.6:1), 150 μL relaxation agent, 150 μL internal standard and 75 μL phosphating reagent were added as test samples. Test conditions: room temperature, 90° pulse angle, 25s pulse interval, 250s signal acquisition time, 61.9ppm scan width. The hydroxyl terminal content is calculated as follows:
其中A(ppm)是PC树脂的端羟基含量;c是内标物的浓度;150(μL)是内标物的体积;100.16(mmg/mmol)是环己醇的摩尔质量;m(mg)是PC树脂的质量;B
1是PC树脂的端羟基峰面积,B
2是环己醇的羟基峰面积。
where A (ppm) is the content of terminal hydroxyl groups of PC resin; c is the concentration of the internal standard; 150 (μL) is the volume of the internal standard; 100.16 (mmg/mmol) is the molar mass of cyclohexanol; m (mg) is the mass of the PC resin; B 1 is the terminal hydroxyl peak area of the PC resin, and B 2 is the hydroxyl peak area of cyclohexanol.
将待测的PBT/PC合金样品置于120℃的除湿干燥箱中烘干4h,然后进行相关性能测试。The PBT/PC alloy samples to be tested were dried in a dehumidifying drying oven at 120 °C for 4 h, and then related performance tests were carried out.
拉伸强度测试:根据标准ISO 527-2:2016注塑拉伸样条,测试拉伸强度S,单位MPa;Tensile strength test: According to the standard ISO 527-2:2016 injection molding tensile splines, test the tensile strength S, the unit is MPa;
热变形温度测试:根据标准ISO 75-2:2013注塑热变形样条,测定1.80Mpa的热变形温度T,单位℃;Heat deformation temperature test: According to the standard ISO 75-2:2013 injection molding heat deformation spline, measure the heat deformation temperature T of 1.80Mpa, the unit is °C;
翘曲度测试:将PBT/PC合金注塑成100*100*1.5mm方板,用1kg重物压住其中一角,用游标卡尺测量对角到水平面的高度h,单位mm。实施例1~18及对比例1~6Warpage test: inject the PBT/PC alloy into a 100*100*1.5mm square plate, press one corner with a 1kg weight, and measure the height h from the diagonal to the horizontal plane with a vernier caliper, in mm. Examples 1-18 and Comparative Examples 1-6
按照表1~表3的配方,制备实施例1~18及对比例1~6,具体制备步骤如下:According to the formulas in Tables 1 to 3, Examples 1 to 18 and Comparative Examples 1 to 6 were prepared, and the specific preparation steps were as follows:
S1.PBT树脂、PC树脂在120~140℃下烘干4~6h;S1. PBT resin and PC resin are dried at 120~140℃ for 4~6h;
S2.将S1.烘干后的PBT树脂、PC树脂与聚碳化二亚胺,抗氧剂混合,从双螺杆挤出机的主喂料口喂料,玻璃纤维从双螺杆挤出机的侧喂料口喂料;S2. Mix the dried PBT resin and PC resin of S1. with polycarbodiimide and antioxidant, and feed the materials from the main feeding port of the twin-screw extruder. The glass fiber is fed from the side of the twin-screw extruder. feeding port feeding;
S3.设置双螺杆挤出机各区的温度为220~250℃,进行挤出,双螺杆挤出机的转速为300-400rpm。;S3. Set the temperature of each zone of the twin-screw extruder to be 220-250° C. to perform extrusion, and the rotational speed of the twin-screw extruder is 300-400 rpm. ;
S4.挤出后进行后处理,得到所述PBT/PC合金。S4. Perform post-processing after extrusion to obtain the PBT/PC alloy.
实施例及对比例的性能测试见表4。The performance test of the embodiment and the comparative example is shown in Table 4.
表1Table 1
表2Table 2
表3table 3
|
对比例1Comparative Example 1
|
对比例2Comparative Example 2
|
对比例3Comparative Example 3
|
对比例4Comparative Example 4
|
PBT树脂1PBT resin 1
|
49.449.4
|
//
|
29.329.3
|
64.364.3
|
PBT树脂3PBT resin 3
|
//
|
49.449.4
|
//
|
//
|
PC树脂1PC resin 1
|
//
|
2020
|
4040
|
55
|
PC树脂3PC resin 3
|
2020
|
//
|
//
|
//
|
玻璃纤维1Fiberglass 1
|
3030
|
3030
|
3030
|
3030
|
聚碳化二亚胺Polycarbodiimide
|
0.50.5
|
0.50.5
|
0.50.5
|
0.50.5
|
抗氧剂1010Antioxidant 1010
|
0.20.2
|
0.20.2
|
0.20.2
|
0.20.2
|
表4Table 4
|
拉伸强度S/MPaTensile strength S/MPa
|
热变形温度T/℃Thermal deformation temperature T/℃
|
翘曲度h/mmWarpage h/mm
|
实施例1Example 1
|
142142
|
150150
|
2.342.34
|
实施例2Example 2
|
144144
|
132132
|
1.241.24
|
实施例3Example 3
|
140140
|
128128
|
0.640.64
|
实施例4Example 4
|
143143
|
125125
|
0.260.26
|
实施例5Example 5
|
130130
|
125125
|
1.021.02
|
实施例6Example 6
|
144144
|
132132
|
1.241.24
|
实施例7Example 7
|
145145
|
143143
|
1.861.86
|
实施例8Example 8
|
148148
|
150150
|
2.442.44
|
实施例9Example 9
|
134134
|
122122
|
1.261.26
|
实施例10Example 10
|
144144
|
132132
|
1.241.24
|
实施例11Example 11
|
144144
|
140140
|
1.241.24
|
实施例12Example 12
|
142142
|
143143
|
1.261.26
|
实施例13Example 13
|
143143
|
131131
|
1.241.24
|
实施例14Example 14
|
143143
|
133133
|
1.261.26
|
实施例15Example 15
|
141141
|
130130
|
1.281.28
|
对比例1Comparative Example 1
|
122122
|
117117
|
1.261.26
|
对比例2Comparative Example 2
|
120120
|
115115
|
1.221.22
|
对比例3Comparative Example 3
|
124124
|
110110
|
0.180.18
|
对比例4Comparative Example 4
|
142142
|
178178
|
3.463.46
|
从实施例2与对比例1、对比例2对比可以看出,当PBT的端羧基含量、PC的酚羟基含量任一超出所述范围,产品的拉伸强度、热变形温度出现明显的下降。From the comparison of Example 2 with Comparative Example 1 and Comparative Example 2, it can be seen that when either the terminal carboxyl group content of PBT or the phenolic hydroxyl group content of PC exceeds the stated range, the tensile strength and heat distortion temperature of the product are significantly decreased.
从对比例3可以看出,当PC的添加量过高,虽然翘曲性能变好,但对拉伸强度、热变形温度迅速下降。从对比例4可以看出,当PBT的添加量过高,组合物翘曲性能迅速下降。It can be seen from Comparative Example 3 that when the amount of PC added is too high, although the warpage performance becomes better, the tensile strength and thermal deformation temperature drop rapidly. It can be seen from Comparative Example 4 that when the amount of PBT added is too high, the warpage performance of the composition decreases rapidly.