Self-healing materials refer to a class of materials that can spontaneously repair cracks and restore to some extent their original state after cracks appear in the material. Not long ago, the synthesis of a copolymer $\bf X$ ($\rm PBA_x-co-PNMA_y$, $co$ represents copolymerization) with self-healing properties was reported:

<MultiModal>![This is a copolymerization reaction, represented in SMILES format as: O=C(C(C)Cl)OCCCCCCN=[N+]=[N-].C=CC(CCCC)=O.C=CC(NCO)=O>>X. The reaction conditions are catalytic amount of $\rm CuCl$, $\rm Me_6TREN$ (tris(2-dimethylaminoethyl)amine), $\rm MeOH$, 60 degrees Celsius.](/media/uploads/79058c31-2e26-459a-8c47-e6bf02cf9a91.png)</MultiModal>

Which of the following statements are incorrect (if statement 1 and statement 2 are incorrect, use "12" to represent it):

1. This is coordination polymerization

2. The only dynamic covalent bonds during the self-healing of $\bf X$ are ether bonds formed by hydroxyl dehydration

3. In the self-healing process, the role of the $\rm BA$ segment is to act as a flexible group to promote the movement of broken chains towards nearby chains, thereby generating dynamic and static hydrogen bonds to heal the damage

4. After the polymer $\bf X$ self-heals in water, the shape and morphology remain unchanged even after soaking in water for 24 hours, because there are a large number of hydrogen bonds in $\bf X$

5. Polymer elasticity $\rm PBA_{0.7}-co-PNMA_{0.3}>PBA_{0.8}-co-PNMA_{0.2}$

6. If $\rm AIBN$ is used to replace $\rm CuCl$ for copolymerization to obtain a new polymer $\bf X'$. Compared with $\bf X$, the distribution of $\rm BA$ fragments and $\rm NMA$ fragments in $\bf X'$ is more random.
自愈材料是指在材料出现裂缝之后，能够自发修补裂缝并在一定程度上恢复原状的一类材料。前不久报道了一种具有自愈性能的共聚物$\bf X$（$\rm PBA_x-co-PNMA_y，co$表示共聚）的合成：

<MultiModal>![这是一个共聚反应，以SMILES格式表示为：O=C(C(C)Cl)OCCCCCCN=[N+]=[N-].C=CC(CCCC)=O.C=CC(NCO)=O>>X。反应条件为催化量$\rm CuCl、Me_6TREN$(三(2-二甲氨基乙基)胺、$\rm MeOH$、60摄氏度。](/media/uploads/79058c31-2e26-459a-8c47-e6bf02cf9a91.png)</MultiModal>

下列说法错误的有（若说法1和说法2错误则用“12”表示）：

1. 这是配位聚合

2. $\bf X$自愈时的动态共价键仅有羟基脱水形成的醚键

3. 在自愈过程中，$\rm BA$片段的作用为作为柔性基团促进破裂链向附近的链的移动，进而产生动态和静态氢键以愈合损伤

4. 聚合物$\bf X$在水中自愈后，即使在水中浸泡24小时后的形状和形态仍保持不变，这是因为$\bf X$中存在大量氢键

5. 聚合物弹性$\rm PBA_{0.7}-co-PNMA_{0.3}>PBA_{0.8}-co-PNMA_{0.2}$

6. 若用$\rm AIBN$取代$\rm CuCl$进行共聚得到新的聚合物$\bf X'$。相比$\bf X$，$\bf X'$中$\rm BA$片段和$\rm NMA$片段的分布更加随机。
All other options are incorrect
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其他选项均不正确
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Statement 1: The reaction is initiated by $\rm CuCl$ capturing $\rm Cl$ to generate free radicals. The polymerization process does not involve coordination reactions and belongs to (living) free radical polymerization. Incorrect.

<Checkpoint>[The reaction is free radical polymerization, statement 1 is incorrect](1)</Checkpoint>

Statement 2: The self-healing ability of $\rm X$ comes from the dynamic covalent bonds and hydrogen bonds between polymer chains. Their existence allows the polymer to continuously interact between chains after fracture, gradually reaching the potential well of deep cross-linking between chains. Among them, the dynamic covalent bond is only the ether bond formed by hydroxyl dehydration. Statement 2 is correct.

<Checkpoint>[The dynamic covalent bond is only the ether bond formed by hydroxyl dehydration. Statement 2 is correct](1)</Checkpoint>

Statement 3: The roles of the two segments in the self-healing process are: $\rm BA$ acts as a flexible group to promote the movement of broken chains to nearby chains, thereby generating dynamic and static hydrogen bonds to heal the damage; $\rm NMA$ provides hydrogen bonds and dynamic covalent bonds to promote chain cross-linking. Statement 3 is correct.

<Checkpoint>[$\rm BA$ acts as a flexible group to promote the movement of broken chains to nearby chains, thereby generating dynamic and static hydrogen bonds to heal the damage. Statement 3 is correct](1)</Checkpoint>

Statement 4: The shape remains unchanged after prolonged immersion in water, which is related to the hydrophobic effect of the $\rm BA$ segment, which can protect the hydrogen bonds between chains from being destroyed, so it will not break again. Statement 4 is incorrect.

<Checkpoint>[The shape remains unchanged after prolonged immersion in water is related to the hydrophobic effect of the $\rm BA$ segment. Statement 4 is incorrect](1)</Checkpoint>

Statement 5: The more flexible $\rm BA$ segments are, the greater the polymer elasticity, $\rm PBA_{0.7}-co-PNMA_{0.3}<PBA_{0.8}-co-PNMA_{0.2}$. Statement 5 is incorrect.

<Checkpoint>[$\rm PBA_{0.7}-co-PNMA_{0.3}<PBA_{0.8}-co-PNMA_{0.2}$. Statement 5 is incorrect](1)</Checkpoint>

Statement 6: When $\rm CuCl$ is used to catalyze the polymerization, $\rm NMA$ has a certain coordination effect with the $\rm Cu$ salt in the system, resulting in a large difference in the reaction rates of the two monomers, so the arrangement will be more ordered; when copolymerized under $\rm AIBN$ catalysis, the two monomers are basically randomly distributed. Statement 6 is correct.

<Checkpoint>[Compared to $\bf X$, the distribution of $\rm BA$ and $\rm NMA$ segments in $\bf X'$ is more random. Statement 6 is correct](1)</Checkpoint>
说法1：该反应为$\rm CuCl$攫取$\rm Cl$产生自由基启动，聚合过程不涉及配位反应，属（活性）自由基聚合，错误

<Checkpoint>[该反应为自由基聚合，说法1错误](1)</Checkpoint>

说法2：$\rm X$的自愈能力来源于聚合物链间的动态共价键和氢键，它们的存在使聚合物在断裂后链间可以不断发生作用，逐渐到达链间深度交联的势阱。其中动态共价键仅有羟基脱水形成的醚键，说法2正确

<Checkpoint>[动态共价键仅有羟基脱水形成的醚键，说法2正确](1)</Checkpoint>

说法3：自愈过程中两种片段的作用分别为：$\rm BA$作为柔性基团促进破裂链向附近的链的移动，进而产生动态和静态氢键以愈合损伤；$\rm NMA$提供氢键和动态共价键以促进链的交联。说法3正确

<Checkpoint>[$\rm BA$作为柔性基团促进破裂链向附近的链的移动，进而产生动态和静态氢键以愈合损伤，说法3正确](1)</Checkpoint>

说法4：在水中长时间浸泡形态不变，这与$\rm BA$片段的疏水作用有关，可以保护链间的氢键不被破坏因此不会重新断裂，说法4错误

<Checkpoint>[在水中长时间浸泡形态不变与$\rm BA$片段的疏水作用有关，说法4错误](1)</Checkpoint>

说法5：柔性的$\rm BA$片段占比越多，聚合物弹性越大，$\rm PBA_{0.7}-co-PNMA_{0.3}<PBA_{0.8}-co-PNMA_{0.2}$，说法5错误

<Checkpoint>[$\rm PBA_{0.7}-co-PNMA_{0.3}<PBA_{0.8}-co-PNMA_{0.2}$，说法5错误](1)</Checkpoint>

说法6：用$\rm CuCl$催化聚合时，$\rm NMA$与体系中的$\rm Cu$盐有一定的配位作用，导致两种单体的反应速率有较大的差异，因此排布会更加有序；$\rm AIBN$催化下共聚时，两种单体基本上随机分布。说法6正确

<Checkpoint>[相比$\bf X$，$\bf X'$中$\rm BA$片段和$\rm NMA$片段的分布更加随机，说法6正确](1)</Checkpoint>