徐州汇亚进出口贸易有限公司成立于2003年（原单位名称：曲阳县诚铭花泥厂），在花卉泡沫行业已有多年的生产经验，在不断研究和实践过程中，不断更新花泥技术和花泥设备，现在已解决了花泥低配置生产设备的弊端。在技术和设备更新的同时，不仅实现了树脂免脱水，还实现了自动连续发泡。从而使整个工艺的两大环节再一次实现了自动化生产，进而大幅度降低了生产成本，大大提升了产品质量，使产品质量更稳定，更容易调控；同时也解决了环保、污染等问题。
一：树脂质量的影响因素
I. Influencing Factors on Resin Quality （ 1 ）甲醛与苯酚的比例 (1) Ratio of formaldehyde to phenol
缩聚反应最初生成 预聚物的 性质取决于甲醛与苯酚的 克分子用量比。当克分子比 F/P ﹤ 1 时，反应的初期生成产物为 邻- 羟甲基苯酚 与 对 - 羟甲基苯酚的混合物。其中以邻 - 羟甲基苯酚的含量 较多，羟甲基苯酚中的羟甲基能与苯酚反应生成各种衍生物。若 F/P ﹥ 2 ，则反应初期生成 多元羟甲基苯酚，经进一步的缩聚，则 交联形成不溶、不熔的树脂。因此 P/F 的值应在 1-2 之间。 The properties of prepolymer initially generated by the polycondensation reaction depend on mol ar ratio of formaldehyde to phenol. If the F/P molar ratio is smaller than 1, the product primarily formed by the reaction will be the mixture of o -(hydroxymethyl)phenol and p - ( hydroxymethyl)phenol , of which the o -(hydroxymethyl)phenol is relatively more and the hydroxymethyl and the phenol in the (hydroxymethyl)phenol can generate a variety of derivatives. If the F/P ratio is greater than 2, multi-hydroxymethyl phenol will be generated at the beginning of the reaction , and will be cross-linked to form insoluble and infusible resin s through further polycondensation . Therefore, the P/F ratio should be 1 - 2 .
（2）反应介质的pH值及碱用量的影响
(2) Influence of pH value of reaction medium and alkali content
苯酚与甲醛反应时反应介质的pH值对反应过程有很大的影响。在酸性或中性介质中，苯酚与甲醛所生成的羟甲基苯酚很不稳定，彼此间与苯酚很快地产生缩聚反应。在碱性介质中，羟甲基苯酚是稳定的，只有升高温度或加入酸性催化剂时，缩聚反应才能继续进行。在碱性介质中，即使苯酚与甲醛的用量比有很大变化时，也只能生成热塑性树脂。
实验中，采用在碱性条件下进行反应，甲醛过量，碱的用量为1.5%。
The pH value of reaction medium during the reaction of phenol and formaldehyde has a significant influence on the reaction process. With an acidic or neutral medium, the hydroxymethyl phenol generated by phenol and formaldehyde is very unstable and will induce the polycondensation reaction with phenol quickly. With an alkaline medium, the hydroxymethyl phenol is stable, and the polycondensation reaction may proceed only when temperature rises or acid catalyst is added. Thermoplastic resins are only generated with the alkaline medium even if the ratio of formaldehyde to phenol has a great change. In the experiment, the reaction takes place under the alkaline condition with excess formaldehyde and 1.5% alkali.
（3）反应时间的影响
(3) Influence of reaction time
苯酚与甲醛在催化剂的作用下进行缩聚反应，反应时间过长，所得高聚物粘度过大，以致影响脱水反应，并使贮存期缩短。若聚合时间过短，反应不完全，产品中游离酚和游离醛的含量增加，收率降低。我们选择首先在 72 ℃左右反应 3.25 小时，使苯酚与甲醛反应形成羟甲基酚，达到要求的分子量及粘度。
Phenol and formaldehyde undergo the poly condensation reaction under the action of catalyst . If the reaction time is too long , the viscosity of the high polymer generated will be too high. As a result , the dehydration reaction will be affected and the storage period will be shortened . If the polymerization time is too short, the reaction will be inadequate , free phenol and free formaldehyde in the product will increase and the yield will decrease. It is chosen to induce the reaction for 3.25 hours at about 72 °C in the beginning, allowing phenol and formaldehyde to form hydroxymethyl phenol, so as to achieve the required molecular weight and viscosity .
二：树脂的性能
II.
Resin Properties
(1) 水含量对树脂折光系数的影响 (1) Influence of water content on resin r efraction coefficient
通过往一定量的树脂中逐渐加水，发现随着水含量的增加，树脂的 折光系数呈线型关系下降， 取 自制的树脂 100 克逐步往其中加水， 所呈现的 加水量与 折光系数的关系如图 1 所示 。 By gradually adding water to a certain amount of resin , it is found that the refraction coefficient of resin declines in a linear pattern as water increases. Take 100g self-made resin and add water to it gradually, as a consequence , the relationship between added water and refraction coefficient is obtained as shown in Fig . 1. Added Water (ml) Fig. 1 Relationship between Water Added to Resin and R efraction C oefficient (2) 水含量对树脂黏度的影响 Influence of water content on resin viscosity 粘度反应了流体的流动行为，是流体的重要物理性能之一。 酚醛树脂的粘度对发交联 时的反应都有很大的影响。是控制酚醛树脂质量的一个重要指标。由于酚醛树脂为 水溶性的，因此水份的含量对粘度的影响较大。随着水份含量的增加，树脂的粘度相应地就要减少，取自制树脂 40 克。往其中逐步加入水，测定其粘度。见图 2 。 V iscosity re flects the flow behavior of a fluid . I t is one of the important physical properties of a fluid. The viscosity of phenolic resin has a great influence on the reaction during cross-link ed foaming . It i s an important ind ex to control the quality of phenolic resin. Since phenolic resin is soluble in water , water content significantly influence s the viscosity. As water content increases, the viscosity of resin lowers accordingly . T ake 40 g self-m ade resin and add water to it gradually to measure its viscosity. See Fig . 2.
Viscosity
Added Water (ml)
Fig. 2 Relationship between Water Added to Resin and Viscosity
三：泡沫的制备
III. Foam Preparation
（1）固化速度对发泡工艺的影响
(I)
Influence of hardening speed on foaming process
热固性酚醛树脂发泡工艺的关键是要使发泡速度与固化速度相适应。若发泡速度小于固化速度，就会发不起来，在泡沫出现之前树脂就完全固化。在32-33℃的环境中，发泡固化速度在8分钟左右为宜。实验表明，常温发泡固化速度在100秒左右为宜；加热发泡固化速度在40～60分钟。
It is the key for the thermosetting phenolic resin foaming process to match the foaming speed with the hardening speed. If the foaming speed is lower than the hardening speed, foam will not generate, and resin will completely be hardened before foam comes out. It is advisable that foaming and hardening is at about 8 minutesat ambient temperature of 32 - 33°C. It is better through the experiment thatfoaming and hardening is at about 100s at normal temperature and at 40 – 60 minutesat high temperature.
（2）树脂的黏度对发泡工艺的影响
(2)
Influence of resin viscosity on foaming process
树脂的粘度对调节泡沫密度有重要的影响。树脂粘度太大，发泡时易使气体逸出，使泡孔变大，甚至穿孔、塌泡；粘度太大，则操作困难，所得泡沫密度太大，不均匀。从树脂的发泡试验结果来看，树脂的粘度在8000～20000厘泊为好。
The resin viscosity has a significant influence on adjusting foam density. If the resin viscosity is too high, the gas is easy to escape during foaming, causing foam to have a large hole, or even be broached out and caved in, and it is also difficult to operate and the foam density is too high and nonuniform. The resin foaming test demonstrates that it is better forthe resin viscosity to be 8000 to 20,000 cps.
（3）固化剂对发泡工艺的影响
(3) Influence of hardener on foaming process
强酸固化剂的腐蚀性较强，发泡不易控制；用弱酸固化剂可以降低腐性，并且发泡过程易于控制。
The stronglyacidic hardener is highly corrosive and it is difficult to control foaming, whereas the weakly acidic hardener can reduce thecorrosivity and it is easy to control foaming process.
固化剂的用量过多时，固化速度过快，泡沫密度大，用量过低时容易出现塌泡等现象。因此必须控制好固化。自制的树脂发泡时，固化剂用量对起泡时间的影响如图 3 表示（ 33 ℃发泡）（常温发泡）。
If the hardener is too much, the hardening speed will be too high and then the density of foam will be high. If the hardener is too little, cavein will easily occur. Therefore, it is a must to control hardening. The influence of hardener amount on foaming time is shown in Fig. 3 during foaming with the self-made resin (foaming at 33°C) (foaming at ambient temperature).
Foaming Time
Hardener (g)
Fig. 3 Relationship between Hardener Amount for Resin Foaming and Foaming Time
发泡剂用量大，泡沫的密度小；发泡剂用量小，则泡沫的密度大。通过调节发泡剂的用量可以获得所需密度的制品。 The much the foaming agent is, the lower the foam density is, and vice versa. The product with required density may be obtained by adjusting the amount of foaming agent.
（4）表面活性剂的种类和用量对泡沫制品的性能有较大的影响
(4) Great influence of type and amount of surfactant on foam product properties
阴离子型的表面活性剂能提高泡沫的开孔率，增加泡沫制品的吸水性。适于作插花用泡沫。而非离子型的表面活性剂能够提高泡沫制品的闭孔率，适宜制备建筑材料及绝热保温材料。
An anionic surfactant can increase the open porosity offoam and the water absorption of foam products. Such foam may be used as the flower arranging foam, whereas a nonionic surfactant can improve the closed porosity of foam products, suitable for the preparation of building materials and insulating materials.
（5）泡沫的孔结构
(5) Pore structure of foam
说明了为什么加热发泡的泡沫各种性能优于常温发泡。得的泡沫，泡孔均匀、细我公司目前采用的是加热发泡。从相显微镜和电子显微镜的照片上可以看出：加热发泡所制腻，结构相比之下，常温发泡的泡孔结构则差得很多，这更直观地说明了为什么加热发泡的泡沫各种性能优于常温发泡。
This part shows the reason thatthe properties of foam formed at high temperature are better than that formedat ambient temperature. Thefoams yielded have uniform and fine pores. Foaming at hightemperature is employed by our company. It can be seen from the photos of phase microscope and electron microscope that the pores by foaming at ambient temperature arepoorer compared with those by foaming at hightemperature that are meticulous, more intuitively illustrating that the properties of foam formed at high temperature are better than that formed at ambient temperature.
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| A. Foaming at Ambient Temperature B. Foaming at High Temperature B. Foam Density: 50.4kg/m2 C. Foam Density: 41.4kg/m2 |
温材料来说 ， 导热系数的大小是一个非常重要的指标。导热系数低，保温效果好，能量损失小。导热系数与泡沫的结构是密切相关关的。目前，酚醛铝箔复合夹芯板的导热系数为 0.028W/MK（ 50℃ 时）。 For the insulating materials, the thermal conductivity is a very important index. If the thermal conductivity is low, a good insulating effect will be obtained and the energy loss will be small. The thermal conductivity is closely related to the foam structure. A t present, the thermal conductivity of p henolic aluminum foil compound sandwich panel is 0.028W/MK (at 50 °C ).
泡沫的导热系数（W/MK）
Thermal conductivity of foam (W/MK)
| 常温发泡 | 加热发泡 | 改性发泡 |
| 0.033 | 0.028 | 0.035 |
2、燃烧性
2.
Combustibility
根据GB2406 -2408-80规定，试样在 25-30㎜高的蓝色火焰（约 10000℃ ）上 烧5 分钟，离开火焰后 2 秒 熄灭者为自熄性材料。我们将 酚醛泡沫在规定火焰上烧 5 秒 后，不燃，延长时间继续烧，仍不燃。可见，它属于自熄性材料。 According to GB2406 -2408-80 , the sample is a s elf-extinguishing material if it is baked on 25-30 mm of blue flame for 5 minutes and goes out 2 seconds after took out from the flame. The p henolic foam is non-combustible after setting it on the specified height of flame for 5 seconds, and still non-inflammable if baked for an extended time. I t can clearly be seen that the phenol ic foam is a s elf-extinguishing material .
3、临界氧指数
3.
Critical oxygen index
材料的临界氧指数是其难燃性的表征。临界氧指数值越大，不易燃烧。难燃性好；反之，临界氧指数值越小，易于燃烧。难燃性差。由于酚醛树脂分子中含有大量苯环，碳原子的比例高，在高温下易于碳化，因此其临界指数值较大。
The critical oxygen index of a material characterizes its flame resistance properties. The higher the critical oxygen index is, the more nonflammable the material is, indicating a higher flame resistance, and vice versa. Since the phenolic resin molecules contain a large number of benzene rings, the proportion of carbon atoms is high and it iseasy to be carboniz ed at high temperature . T herefore , the critical index of phenolic resin is relatively high. 为加强酚醛 泡沫塑的阻燃性能，我们选用 A1 （ OH ） 氯化磷 酚酯 TCEP101， 505 等 阻燃剂进行实验，结果见表 3 。 To improve the flame resistance properties of phenolic plastic foam , flame retardant s such as a luminum hydroxide , p hosphorus trichloride , phenolic ester , TCEP101 and 505 are selected to carry out the experiment with results shown in Table 3.
4、泡沫的吸水率
4.
Water absorption of foam
吸水率的高低决定了板材的防潮性能。我公司的产品吸水率＜2%。
The water absorption determines the moisture resistance of plates. The water absorption of our company’s products is smaller than 2%.
泡沫的孔结构对泡沫的吸水率影响很大。孔大，开孔率高，粗糙，吸水率就大；相反，吸水率就小。
The pore structure of foam greatly influences its water absorption. If the pores are big, the open porosityis high, the foam is rough and then the water absorption is high, and vice versa.
泡沫的吸水率随容重的变化而变化，容重越大，泡孔越细密，吸水率越小。影响较大的是发泡配方工艺。对于加热发泡，树脂固化得比较好，泡沫闭孔率较高，所以吸水率比常温发泡发低，吸水量还不到原来的一半。
The water absorption of foam changes as the volume weight changes. The heavier the volume weight is, the more meticulous the foam pores are and the lower the water absorption is. What is greatly influenced is the foam formulation process. For foaming at high temperature, the resin is well hardened and the closed porosity of foam is relatively high. Therefore, the water absorption for foaming at high temperature is smaller than that for foaming at ambient temperature and the water absorption is less than half of the original.
5、吸声性能
5.
Sound absorption
酚醛泡沫的优良吸声性能，赋予它广泛的用途。开孔型的泡沫结构有利于吸声，在气流中，由于受激振动空气的摩擦，使声波转换为热量，从而被吸收。
A wide range of application is contributed to phenolic foam due to its good sound absorption. The foam structure with open pore is conducive to sound absorption. The friction of induced vibration air in the air flow makes sound waves converted into heat, with the result that absor ption is achieved . 酚醛泡沫的吸声性能用吸声系数来表征， 实验测试的结果如表 5 所示。 作为比较，列举出硬质聚氨酯泡沫塑料的吸声系数见表 6 。 The sound absorption of phenolic foam is characterized by the absorption coefficient . The test results are shown in Table 5. In comparison, t he absorption coefficient of rigid polyurethane foam plastics is listed in Table 6 .
6、热稳定性
6.
Thermal stability
按前述方法，我们测定了酚醛泡沫的热稳定性，烘烤 48 小时后的结果如表 7 所示。表中的数据表明，泡沫的密度越大，热稳定性越好；密度越小，热稳定性越差。这是因为当泡沫的密度较低时，其表面积就大，与空气中的氧接触的可能性增加，在高温下易于氧化而受到破坏。所以其热稳定性较差。此外，延长烘烤时间，泡沫的体积和重量变化起来越小，**趋于稳定。
The thermal stability of phenolic foam is tested by baking for 48 hours using the said method with the results shown in Table 7. The data in the table shows that the higher the foam density is, the higher the thermal stability is; the lower the foam density is, the lower the thermal stability is. This is because the surface area is large and the possibility to contact with oxygen in the air increases if the foam density is low; the foam will be damaged as it is easy to be oxidized at high temperature, thus, the thermal stability is poor. Besides, the more the baking time is extended, the less the volume and the weight of foam will change until it trends to be stable.
7、热分析
7.
Thermal analysis
图8为酚醛泡沫在空气中的T/GB谱图
Fig. 8 shows the T/GB spectrogram of p henolic foam in the air 一般把该图分为四个阶段。**阶段为 0 ～ 100 ℃ ，在此温度下，酚醛泡沫体中的 低分子物受热挥发，它们是水份、甲醛、苯酚、固化剂和发泡剂的残留物等。第二阶段为 100 ～ 170 ℃ ，酚醛树脂的 氢键重新组合，形成羟基。在第三阶段（ 170 ～ 280 ℃ ） 主要是链 C-O-C 的断裂。第四个阶段（ 280 ～ 600 ℃ ）为羟基结构的破坏，同时释放出 CO 和 CO 气体，以及其它挥发性的脂肪族的有机物，如 CH ，此外，在 120 ～ 250 ℃ 之间，酚醛树脂还发生降解和交联的竞争反应。 Generally, the spectrogram is divided into 4 stages. T he first stage is 0 - 100 °C , at which the compounds with l ow molecular weight (i.e. residue of water, formaldehyde, phenol, hardener and foaming agent ) in the phenolic foam will be volatiliz ed by being heated . The second stage is 100 to 170 °C, at which the hydrogen bond s of phenolic resin will be recombined to form hydroxyl. During the third stage (170 - 280 °C), the main issue is that the chain of C - O - C will be fracture d . During t he fourth stage (280 - 600 °C), h ydroxyl structure destroyed and CO , CO gas , and other volatile aliphatic organic compounds such as CH will be released simultane ously. I n addition, phenolic resin will undergo competitive reaction of degradation and cross - linking between 120 ~ 250 °C.
同时从TG谱图中可以看出，酚醛泡沫的耐热性能良好，使用温度高，在 180℃以下失重量很小。
It can be seen from the TG spectrogram that phenolic foam has a high heat resistance, high service temperature and little weight loss under 180 °C.
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